TWI622858B - Positive radiation-sensitive resin composition, cured film, method for forming the same, semiconductor element, and display element - Google Patents

Abstract

An object of the present invention is to provide a hardened film that has excellent surface hardness and can satisfy general characteristics such as sensitivity, development adhesion, chemical resistance, heat resistance, transmittance, and relative dielectric constant, and has storage stability. Excellent thermosetting resin composition for curing film formation, negative radiation sensitive resin composition, and positive radiation sensitive resin composition.

The present invention is a thermosetting resin composition for forming a cured film, which contains [A1] a polymer having a structural unit (I) and a structural unit (II-1), the structural unit (I) comprising The structural unit (II-1) includes at least one of a group represented by the formula (1) and a group represented by the following formula (2), and the structural unit (II-1) includes a crosslinkable group (a1).

In addition, the present invention is a negative radiation-sensitive resin composition comprising: [A2] a polymer having a structural unit (I) and a structural unit (II-2), the structural unit (I) comprising At least one of the group represented by the formula (1) and the group represented by the following formula (2): The unit (II-2) contains a crosslinkable group (a2); [B] a polymerizable compound having an ethylenically unsaturated bond; and [C] a radiation-sensitive polymerization initiator.

Furthermore, the present invention is a positive-type radiation-sensitive resin composition containing: [A3] a polymer having a structural unit (I) and a structural unit (II-3), the structural unit (I) comprising At least one of a group represented by the following formula (1) and a group represented by the following formula (2), and the structural unit (II-3) includes a cyclic ether structure or a cyclic carbonate Structure; and [G] acid generator.

In Formula (1), R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. In formula (2), R ³ and R ⁴ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. The crosslinkable group (a1) is preferably at least one selected from the group consisting of an ethylene oxide group and an oxetanyl group.

Description

Positive radiation-sensitive resin composition, cured film, method for forming the same, semiconductor element, and display element

The present invention relates to a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a cured film, a method for forming the same, a semiconductor element, and a display element.

In recent years, flexible displays such as electronic paper have attracted attention, and as substrates for flexible displays, research has been conducted on plastic substrates obtained using polyethylene terephthalate. This substrate causes stretching or shrinkage during heating. Therefore, research is being conducted to reduce the temperature of the manufacturing process. In particular, it is required to reduce the firing temperature in the step of forming a hardened film such as an interlayer insulating film which is the highest temperature in the manufacturing process.

As a material of the cured film which can be reduced in temperature as such, a radiation-sensitive resin composition having a small number of steps at the time of pattern formation and high surface hardness is used. For example, a copolymer containing a carboxyl group and an epoxy group is known The radiation-sensitive resin composition of the object is configured such that the surface hardness of the cured film can be obtained by reacting the carboxyl group with an epoxy group (see Japanese Patent Application Laid-Open No. 2001-354822).

However, in the radiation-sensitive tree containing the copolymer described above, In the lipid composition, the carboxyl group and the epoxy group may react when the radiation-sensitive resin composition is stored. As a result, there is a possibility that the viscosity may increase and the storage stability may decrease.

Therefore, there is a need for a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, and a positive radiation-sensitive resin composition, which can form an excellent surface hardness and sufficiently satisfy sensitivity and development adhesion. , Chemical resistance, heat resistance, transmittance, and relative properties of the cured film, and has excellent storage stability.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-354822

The present invention has been completed based on the above circumstances, and an object thereof is to provide a resin composition for forming a cured film, a negative radiation-sensitive resin composition, and a positive radiation-sensitive resin composition, which can be formed to have excellent surface hardness and A cured film that satisfies general characteristics such as sensitivity, development adhesion, chemical resistance, heat resistance, transmittance, and relative permittivity, and has excellent storage stability.

An invention developed to solve the above-mentioned problems is a thermosetting resin composition for curing film formation (hereinafter, also referred to as "resin composition for curing film (1)"), which contains: [A1] I) and a polymer (hereinafter, also referred to as “[A1] polymer”) and a structural unit (II-1) containing a group selected from the group consisting of a group represented by the following formula (1) And at least one of the group of groups represented by the following formula (2), the structural unit (II-1) contains a crosslinkable group (a1), (In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, among R ¹ and R ² , At least one is a fluoroalkyl group having 1 to 4 carbon atoms.

In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms).

In addition, another invention completed to solve the above-mentioned problems is a method for forming a cured film, which has the following steps: (1) a step of forming a coating film on a substrate using the resin composition (1) for forming the cured film; and (2) A step of heating the coating film (hereinafter, also referred to as a "method for forming a cured film (1)").

In addition, another invention completed to solve the above-mentioned problems is a negative-type radiation-sensitive resin composition (hereinafter, also referred to as "negative-type radiation-sensitive resin composition (2)"), which contains: [A2] having a structure Polymer of unit (I), structural unit (II-2) Hereinafter, it is also referred to as "[A2] polymer"), and the structural unit (I) includes a group selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) At least one of the group, the structural unit (II-2) contains a crosslinkable group (a2); [B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter, also referred to as "[B] polymerizable compound "); And [C] a radiation-sensitive polymerization initiator.

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, among R ¹ and R ² , At least one is a fluoroalkyl group having 1 to 4 carbon atoms.

In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms).

In addition, another invention completed to solve the above-mentioned problems is a method for forming a cured film (hereinafter, also referred to as a "method for forming a cured film (2)"), which has the following steps: (1) using the negative-type radiation (2) a step of forming a coating film on a substrate; (2) a step of irradiating a part of the coating film with radiation; (3) a step of developing the coating film irradiated with radiation; and (4) A step of heating the developed coating film.

Furthermore, other inventions made in order to solve the above-mentioned problems include inventions including a cured film (hereinafter, also referred to as a "cured film (1)") formed from the resin composition (1) for forming a cured film, and a negative type. A cured film (hereinafter, also referred to as a "cured film (2)") formed of the radiation-sensitive resin composition (2), a semiconductor element including the cured film, and a display element including the semiconductor element.

The "crosslinkable group" refers to a group capable of forming a covalent bond between the same or different molecules.

An invention developed to solve the above-mentioned problems is a positive-type radiation-sensitive resin composition containing: [A3] a polymer having a structural unit (I) and a structural unit (II-3) (hereinafter, also referred to as "[ A3] polymer "), the structural unit (I) contains at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), The structural unit (II-3) includes a cyclic ether structure or a cyclic carbonate structure; and a [G] acid generator.

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, among R ¹ and R ² , At least one is a fluoroalkyl group having 1 to 4 carbon atoms.

In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms).

In addition, other inventions made to solve the above-mentioned problems include inventions including a cured film (hereinafter, also referred to as a "cured film (3)") formed of the positive radiation-sensitive resin composition, and a semiconductor including the cured film And a display element including the semiconductor element.

Furthermore, another invention completed in order to solve the above-mentioned problems is a method for forming a cured film (hereinafter, also referred to as a "method for forming a cured film (3)"), which has the following steps: (1) using the positive type A step of forming a coating film on a substrate with a radiation resin composition; (2) a step of irradiating a part of the coating film with radiation; (3) a step of developing the coating film irradiated with radiation; and (4) A step of heating the coated film after the development.

The present invention can provide a thermosetting resin composition for forming a cured film, a negative-type radiation-sensitive resin composition, and a positive-type radiation-sensitive resin composition, which can be formed to have excellent surface hardness and sufficiently satisfy sensitivity, development adhesion Film with general properties such as chemical resistance, chemical resistance, heat resistance, transmittance, and relative dielectric constant, and is stable in storage Excellent qualitative. Therefore, the thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a thermosetting resin composition formed from this cured film, and a negative radiation-sensitive resin The hardened film formed from the resin composition and the positive radiation-sensitive resin composition, the semiconductor element and the display element, and the method for forming the hardened film can be suitably used in manufacturing processes of electronic devices such as flexible displays.

[Form of Implementing Invention]

<Resin composition (1) for curing film formation>

The resin composition (1) for forming a cured film of the present invention contains a [A1] polymer. The resin composition (1) for forming a cured film may contain other components other than the [A1] polymer within a range that does not impair the effects of the present invention.

The resin composition (1) for forming a cured film contains a [A1] polymer and is a so-called thermosetting resin composition that is hardened by crosslinking caused by heating. Each component is described in detail below.

<[A1] polymer>

[A1] The polymer is a polymer having a structural unit (I) and a structural unit (II-1). [A1] The polymer may have a structural unit (III) and a structural unit (IV) as long as the effect of the present invention is not impaired. By providing the [A1] polymer with a structural unit (I) and a structural unit (II-1), the resin composition (1) for forming a cured film can be formed to have excellent surface hardness and can be formed. A cured film that satisfies general properties such as chemical resistance, heat resistance, transmittance, and relative dielectric constant, and has excellent storage stability. This is presumably because, upon heating, the hydroxyl group in the group represented by formula (1) and / or (2) contained in the structural unit (1) and the hydroxyl group contained in the structural unit (II-1) were The cross-linking group (a1) reacts, and the excellent surface hardness of the cured film is obtained by the formation of a strong cross-linked structure. The above-mentioned reaction is not easy to proceed at normal temperature. As a result, thickening during storage can be suppressed and good results can be obtained Storage stability. The [A1] polymer may have two or more kinds of each structural unit.

[Construction unit (I)]

The structural unit (I) is a structural unit including at least one selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2).

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² is a fluoroalkyl group having 1 to 4 carbon atoms.

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and secondary butyl. , Tertiary butyl, etc.

A fluoroalkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ described above is a group in which a part or all of hydrogen atoms in the alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. Examples of the fluoroalkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, and 2,2,2. -Trifluoroethyl, perfluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluoroethylmethyl, perfluoropropyl, 2,2,3,3,4,4-hexafluoro Butyl, perfluorobutyl, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl, etc. Among them, the fluoroalkyl group having 1 to 4 carbon atoms is preferably a trifluoromethyl group.

Examples of the halogen atom represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, the halogen atom is preferably a fluorine atom.

As a structural unit (I) containing a group represented by the said Formula (1), the structural unit represented by following formula (1a) and (1b) is preferable.

In the formulae (1a) and (1b), R is each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ¹ and R ^{2 are} defined in the same manner as in the above formula (1). R ⁵ and R ⁶ are each independently a (n + 1) -valent organic group. n are each independently an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ and R ² may be the same or different.

Examples of the (n + 1) -valent organic group represented by R ⁵ and R ⁶ include (n + 1) -valent chain hydrocarbon groups having 1 to 20 carbon atoms, and those having 3 to 20 carbon atoms. (n + 1) -valent alicyclic hydrocarbon group, or (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a chain-like hydrocarbon group having 1 to 20 carbon atoms in combination, and 3 to 20 carbon atoms Among the alicyclic hydrocarbon group and the aromatic hydrocarbon group having 6 to 20 carbon atoms, two or more kinds of (n + 1) -valent groups and the like. However, some or all of the hydrogen atoms possessed by these groups may be substituted.

Examples of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms include a group in which n hydrogen atoms are removed from a linear or branched alkyl group having 1 to 20 carbon atoms. .

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, and 1 -Methylpropyl, tertiary butyl, etc.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a group in which n hydrogen atoms are removed from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like.

Examples of the (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms include a group obtained by removing n hydrogen atoms from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

The R ^{5 is} preferably methylene, ethylidene, 1,3-propylidene, or 1,2-propylidene, tetramethylene, pentamethylene, and hexamethylene. Methylene, heptamethylene, octamethylene, decamethylene, decamethylene, undecyl methylene, dodecyl methylene, tridecyl methylene, tetradecyl methylene, pentamethylene , Hexamethylene, heptamethylene, octamethylidene, 19-methylene, icosyl, 1-methyl-1,3-propyl, 2-methyl-1 3,3-propyl, 2-methyl-1,2-propyl, 1-methyl-1,4-butyl, 2-methyl-1,4-butyl, metamethylene Saturated chain hydroxyl groups such as ethylidene, ethylidene propyl, 2-ethylidene propyl, etc., cyclobutylene such as 1,3-cyclobutylene, and ring such as 1,3-cyclopentylyl Cyclohexyl, such as pentyl, 1,4-cyclohexyl, etc., Cycloalkyl, etc., such as cyclooctyl, 1,5-cyclooctyl, etc., Monocyclic hydroxyl groups, 1,4- Nodyl, 2,5-Dyridinyl, or 2,6-Dyridinyl, etc.Dydyl, 1,5-Danadamantyl or 2,6-Danadamantyl, etc. Polycyclic hydroxyl groups such as adamantyl, 1,3,5-cyclohexanetriyl, etc. 1,3-phenylene, 1,4-phenylene and other aromatic hydroxyl groups, or groups obtained by combining them, more preferably ethyl, 1,2-phenylene, 2, 5-norbornyl, 1,4-phenylene, 1,3,5-cyclohexanetriyl. The R ^{6 is} preferably a divalent aromatic hydrocarbon group such as 1,3-phenylene or 1,4-phenylene, and more preferably 1,4-phenylene.

As a structural unit (I) containing a group represented by the said Formula (2), the structural unit represented by following formula (2a) and (2b) is preferable.

In the formulae (2a) and (2b), R is defined in the same manner as the formulae (1a) and (1b). R ³ and R ^{4 are} defined in the same manner as in the above formula (2).

Examples of the structural unit (I) include structural units represented by the following formulae (I-1) to (I-15).

In the above formula, R is defined in the same manner as in the formulas (1a), (1b), (2a), and (2b). Among these, as the structural unit (I), the structural units represented by the formulae (I-1) to (I-6), (I-9), and (I-11) to (I-13) are preferred. From the viewpoint of alkali developability and / or thermosetting property, the structural units represented by the formulae (I-1) to (I-6) are more preferred.

The content ratio of the structural unit (I) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol or more and 80 mol% or less, with respect to all the structural units constituting the [A1] polymer. It is more preferably 30 mol% or more and 70 mol% or less. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Construction unit (II-1)]

The structural unit (II-1) is a structural unit containing a crosslinkable group (a1).

Examples of the crosslinkable group (a1) include an epoxyethyl group (1,2-epoxy structure), an oxycyclobutane group (1,3-epoxy structure), and a cyclic carbonate. Group, (meth) acrylfluorenyl and the like.

Examples of the structural unit (II-1) containing an epoxyethyl group include a structural unit represented by the following formulae (II'-1) to (II'-5).

Examples of the structural unit (II-1) containing an oxycyclobutane group include the structural units represented by the following formulae (II'-6) to (II'-9).

Examples of the structural unit (II-1) containing a cyclic carbonate group include the structural units represented by the following formulae (II'-10) to (II'-14).

In the formulae (II'-1) to (II'-14), R ⁷ is a hydrogen atom, a methyl group, or a trifluoromethyl group.

In addition, as a structural unit containing a (meth) acrylfluorenyl group (II-1) For example, structural units derived from a monomer compound such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylic acid can be listed. Ester, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (meth) acrylate compounds such as tripropylene glycol diacrylate, such as (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tris (meth) acrylate compounds such as neopentaerythritol tri (meth) acrylate, tetra (meth) acrylate compounds such as neopentaerythritol tetra (meth) acrylate, dipentaerythritol five Monomer compounds such as penta (meth) acrylate compounds such as (meth) acrylates.

Among them, the crosslinkable group (a1) is preferably at least one selected from the group consisting of ethylene oxide and oxycyclobutane. This can further improve the chemical resistance of the formed cured film.

The content ratio of the structural unit (II-1) is preferably 1 mol% or more and 70 mol% or less, and more preferably 5 mol% or more and 50 mol relative to all the structural units constituting the [A1] polymer. % Or less, more preferably 10 mol% or more and 30 mol% or less. When the content ratio of the structural unit (II-1) is within the above range, storage stability and the like can be effectively improved.

[Construction unit (III)]

[A1] The polymer may have a structural unit (III) described later. The content ratio of the structural unit (III) can be appropriately determined within a range that does not impair the effects of the present invention.

[Construction unit (IV)]

[A1] The polymer may have a structural unit (IV) described later. By having the [A1] polymer having a structural unit (IV), the resin composition (1) for forming a cured film can adjust the glass transition temperature of the resin, which can improve the melt flowability during thermal curing or the obtained Mechanical strength and chemical resistance of the cured film.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, relative to all the structural units constituting the [A1] polymer. It is more preferably 3 mol% or more and 60 mol% or less. When the content ratio of the structural unit (IV) is within the above range, chemical resistance can be effectively improved.

<[A1] Synthesis method of polymer>

[A1] A polymer can be produced, for example, by polymerizing a monomer corresponding to a predetermined structural unit in a suitable solvent using a radical initiator. For example, it is preferable to synthesize by a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to perform a polymerization reaction; a solution containing the monomer and Method for individually adding a solution containing a radical initiator to a solution containing a reaction solvent or a monomer to perform a polymerization reaction; a plurality of solutions containing respective monomers and a solution containing a radical initiator are individually separated A method such as a method of dropping polymerization into a solution containing a reaction solvent or a monomer to perform a polymerization reaction.

The reaction temperature in these methods may be appropriately determined depending on the type of the initiator. It is usually 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, and more preferably 50 ° C to 140 ° C. The dropping time depends on the reaction temperature and the starting agent. The conditions such as the kind and the monomer to be reacted differ, but it is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. The total reaction time including the dropwise addition time also varies depending on conditions similar to the dropwise addition time, but it is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.

Examples of the radical initiator used in the polymerization include azobisisobutyronitrile (AIBN) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). ), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2 -Methylpropionitrile) and the like. These initiators can be used alone or in combination of two or more.

The polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibitory effect, a mercapto compound having a chain transfer effect, and the like) and can dissolve the monomer. Examples of the polymerization solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amidine-based solvents, ester / lactone-based solvents, and nitrile-based solvents. These solvents may be used alone or in combination of two or more.

The polymer obtained by the polymerization reaction can be recovered by a reprecipitation method. That is, after the polymerization reaction is terminated, the target polymer is recovered as a powder by adding the polymer solution to a reprecipitation solvent. As a reprecipitation solvent, alcohols, alkanes, etc. can be used individually or in mixture of 2 or more types. In addition to the reprecipitation method, the polymer can be recovered by removing low-molecular components such as monomers and oligomers through a liquid separation operation, a column operation, and an ultrafiltration operation. When the polymerization solvent is the same as the solvent of the resin composition (1) for forming a cured film to be prepared, the obtained polymer solution may be used as it is, or may be applied to the obtained polymer solution. A solvent is added to the polymer solution, and the polymer solution is used for preparing a resin composition (1) for forming a cured film.

In the polymerization reaction for producing the [A1] polymer, a molecular weight modifier can be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, Thiols such as mercaptoacetic acid, xanthates such as dimethylxanthate sulfide, diisopropylxanthate disulfide, terpinolene, α-methylstyrene dimer Wait.

[A1] The polystyrene-equivalent weight average molecular weight (Mw) of the polymer obtained by gel permeation chromatography (GPC) is not particularly limited, but it is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. The ratio (Mw / Mn) of Mw of the [A1] polymer to the polystyrene-equivalent number average molecular weight (Mn) obtained by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less. .

<Other ingredients>

Examples of other components that may be contained in the cured film-forming resin composition (1) include, in addition to the solvents described below, [D] antioxidants, [E] surfactants, and [F] ] Adhesion aids, etc. Moreover, in this resin composition (1) for hardening film formation, each of the said components can be used individually or in combination of 2 or more types.

<[D] Antioxidant>

[D] Antioxidant is a component that can decompose free radicals generated by exposure or heating or peroxides generated by oxidation to prevent bond cleavage of polymer molecules. As a result, the obtained cured film can be prevented The occurrence of oxidative degradation over time can suppress, for example, a change in film thickness of a cured film.

Examples of the [D] antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among these, as the [D] antioxidant, a compound having a hindered phenol structure is preferable.

Examples of the compound having a hindered phenol structure include neopentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylene glycol. Alcohol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, Ginseng- (3,5-di-tertiarybutyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tertiarybutyl 4-Hydroxyphenylpropanamide), 3,3 ', 3', 5 ', 5'-hexa-tertiary-butyl-a, a', a '-(mesitylene-2,4,6 -Triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene Bis (pentyloxyethyl) bis [3- (5-tertiarybutyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tri Butyl-4-hydroxyphenyl) propionate], 1,3,5-gins [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3 , 5-three -2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tertiary-butyl-4- (4,6-bis (octylthio) -1,3,5-tris 2-ylamino) phenol, 1,3,5-trimethyl-2,4,6-para (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, 2,6- Di-tertiary butyl-4-cresol and the like.

Commercial product as the compound having the hindered phenol structure For example, Adekastab AO-20, same AO-30, same AO-40, same AO-50, same AO-60, same AO-70, same AO-80, and AO-330 (above, made by ADEKA) , SumilizerGM, same GS, same MDP-S, same BBM-S, same WX-R, same as GA-80 (above, made by Sumitomo Chemical), IRGANOX1010, same 1035, same 1076, same 1098, same 1135, same 1330, Same as 1726, Same WL, Same 245, Same 259, Same 3114, Same 565, Same 295 (above, made by BASF), Yoshinox BHT, Same BB, Same 2246G, Same 425, Same 250, Same 930, Same SS , Same as TT, same as 917, same as 314 (above, manufactured by API Corporation), etc.

Among these, as the compound having a hindered phenol structure, neopentaerythritol [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, 2,6-di-tertiarybutyl-4-cresol.

The content of the [D] antioxidant is preferably 0.001 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the [A1] polymer. By making the content of the [D] antioxidant into the above range, it is possible to effectively prevent oxidative degradation of the obtained cured film with time.

<[E] Surfactant>

[E] A surfactant is a component which improves film formation. Examples of the [E] surfactant include a fluorine-based surfactant, a polysiloxane-based surfactant, and other surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain, and a side chain, and examples thereof include 1,1,2,2- Tetrafluoro-n-octyl (1,1,2,2- Tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol bis (1,1,2,2,3,3-hexafluoro- N-pentyl) ether, octaethylene glycol bis (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoro-n-pentyl) Yl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, sodium perfluoron-dodecanesulfonate, 1,1,2,2,3,3-hexafluoron Decane, 1,1,2,2,8,8,9,9,10,10-decafluoron-dodecane or sodium fluoroalkylbenzene sulfonate, sodium fluoroalkyl phosphate, fluoroalkyl carboxylic acid Sodium, diglycerol (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanol, perfluoroalkyl Alkoxylates, fluoroalkyl carboxylates, and the like.

Examples of commercially available products of the above-mentioned fluorine-based surfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), Megafac F142D, same F172, same F173, same F183, same F178, same F191, and same F471, same as F476 (above, manufactured by Daikoku Ink Chemical Industry), Fluorad FC-170C, as -171, as -430, as -431 (above, made by Sumitomo 3M), Surflon S-112, as -113, and- 131, same -141, same -145, same -382, same -101, same -102, same -103, same -104, same -105, same -106 (above, Asahi Glass), Eftop EF301, same 303, Same as 352 (above, new Akita Kasei), Ftergent FT-100, same -110, same -140A, same -150, same -250, same -251, same -300, same -310, same -400S, FTX- 218, same as -251 (above, made by NEOS), etc.

Examples of commercially available products of the above-mentioned polysiloxane surfactants include Toray silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, Same as SZ-6032, same as SF-8428, same as DC-57 Same as DC-190 (above, manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by GE Toshiba Silicone), organic silicon oxygen Alkane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene-n Polyoxyethylene aryl ethers such as octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, etc., polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate, etc. Non-ionic surfactants.

Examples of commercially available products of the other surfactants mentioned above include (meth) acrylic copolymer Polyflo No. 57 and No. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).

The content of the [E] surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the [A1] polymer. When the content of the [E] surfactant is in the above range, the film-forming properties can be effectively improved.

<[F] Adhesion aid>

[F] Adhesion assistant is a component that improves the adhesion between the obtained cured film and the substrate. The [F] adhesion aid is preferably a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, or an ethylene oxide group.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxy Silicon Alkane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The content of the [F] adhesion aid is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 15 parts by mass, based on 100 parts by mass of the [A1] polymer.

<Method for preparing the resin composition (1) for forming a cured film>

The resin composition (1) for forming a cured film of the present invention can be prepared by mixing the [A1] polymer with other components as necessary, preferably by dissolving in a suitable solvent. The prepared resin composition (1) for forming a cured film is preferably filtered with a filter having a pore size of about 0.2 μm, for example.

As the solvent used for the preparation of the resin composition (1) for forming a cured film, those components contained in the resin composition (1) for forming a cured film can be used to uniformly dissolve or disperse each component and not to react with the above components. . Examples of such solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, amidine-based solvents, ester-based solvents, and hydrocarbon-based solvents.

Examples of the alcohol-based solvent include, for example, a monohydric alcohol-based solvent, including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, and n-pentanol. , Isoamyl alcohol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol Alcohol, secondary heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, di Undecyl alcohol, trimethylnonanol, secondary tetradecanol, secondary heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethyl ring Hexanol, benzyl alcohol, diacetone alcohol, etc. Examples of the polyol-based solvent include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, and 2, 5-Hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc., as the polyol partial ether system Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and ethylene glycol. Diethylene glycol mono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono Hexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol. Diethyl ether, tetrahydrofuran, etc.

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, and ethyl N-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4- Pentanedione, acetone acetone, acetophenone, etc.

Examples of the amidamine-based solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, and N, N-diethylformamide. Amidoamine, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropylamine, N-methylpyrrolidone, and the like.

Examples of the ester-based solvent include methyl acetate. , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, n-pentyl acetate, secondary amyl acetate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl ring acetate Hexyl ester, n-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol acetate Alcohol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol acetate Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriacetate Ethylene glycol, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, milk Ethyl, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

Examples of the hydrocarbon-based solvent include, as examples of the aliphatic hydrocarbon-based solvent, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, and 2,2,4-trimethylpentane. Alkanes, n-octane, isooctane, cyclohexane, methylcyclohexane, etc. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, and trimethylbenzene. , Methyl ethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene and the like.

The solvent may further contain hexanoic acid and caprylic acid. , Ethylene carbonate, propylene carbonate and other high boiling point solvents.

<Method for Forming Hardened Film (1)>

The method (1) for forming a cured film of the present invention includes the following steps: (1) using the resin composition (1) for forming a cured film to form a coating film on a substrate (hereinafter, also referred to as "step (A1) "); And (2) a step of heating the coating film (hereinafter, also referred to as" step (A2) ").

Since the resin composition (1) for forming a cured film has the above-mentioned properties, the method (1) for forming a cured film according to the present invention can form a resin that satisfies heat resistance, chemical resistance, transmittance, and relative dielectric constant. A hardened film with general characteristics and excellent surface hardness. Hereinafter, each step will be described in detail.

[Step (A1)]

In this step, a coating film is formed on the substrate using the resin composition (1) for forming a cured film. Specifically, the solution of the resin composition (1) for forming a cured film is applied to the surface of the substrate, and it is preferable to form a coating film by removing the solvent by pre-baking. Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate obtained by forming various metal thin films on their surfaces. Examples of the plastic substrate include plastics including polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether fluorene, polycarbonate, and polyimide. Resin substrate.

As a coating method, for example, a suitable method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be adopted. Among these, as the coating side The method is preferably a spin coating method, a bar coating method, or a slit die coating method. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like. For example, it can be set at 60 ° C. to 130 ° C. for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm as a value after pre-baking.

[Step (A2)]

In this step, the coating film is hardened by heating. The heating method is not particularly limited, but for example, heating can be performed using a heating device such as an oven or a hot plate. The heating temperature in this step is preferably 200 ° C or lower. Since the heating can be performed at such a low temperature, the method (1) for forming a cured film can be applied to a cured film such as an interlayer insulating film on a plastic substrate for a flexible display. The heating temperature is more preferably 120 ° C to 180 ° C, and still more preferably 120 ° C to 150 ° C. The heating time varies depending on the type of heating equipment. For example, it can be set to 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes to 80 minutes when heat treatment is performed in an oven. More preferably, it is within 30 minutes when heat processing is performed on a hot plate, and within 60 minutes when heat treatment is performed in an oven. By doing so, a hardened film (1) such as a target interlayer insulating film can be formed on the substrate.

<Hardened film (1)>

The cured film (1) of the present invention is formed from the resin composition (1) for forming a cured film. The method for forming the cured film (1) is not particularly limited, but it is preferably formed by using the method (1) for forming the cured film described above. Since the cured film (1) is formed of the resin composition (1) for forming a cured film, it has excellent surface hardness and can sufficiently satisfy chemical resistance and heat resistance , Transmittance and relative permittivity. Since this cured film (1) has the above-mentioned characteristics, it is suitable as, for example, an interlayer insulating film, a spacer, a protective film, a colored pattern for a color filter, etc. of a display element.

<Negative radiation-sensitive resin composition (2)>

The negative radiation-sensitive resin composition (2) of the present invention contains [A2] a polymer, [B] a polymerizable compound, and [C] a radiation-sensitive polymerization initiator. In addition, the negative radiation-sensitive resin composition (2) may contain [D] an antioxidant as a preferred component. Furthermore, this negative radiation-sensitive resin composition (2) may contain arbitrary components other than [A] component-[D] component in the range which does not impair the effect of this invention.

The negative-type radiation-sensitive resin composition (2) is a so-called negative-type sensor having negative characteristics because it contains [A2] polymer, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator. A radiation resin composition, that is, a portion irradiated with radiation (exposed portion) is hardened by polymerization, and development is performed with an alkali developing solution. The portion other than the exposed portion (unexposed portion) is dissolved and removed to form a pattern. Negative radiation-sensitive resin composition. Therefore, the negative radiation-sensitive resin composition (2) can form a patterned cured film. Each component is described in detail below.

<[A2] polymer>

[A2] The polymer is a polymer having a structural unit (I) and a structural unit (II-2). The [A2] polymer may have a structural unit (III) and a structural unit (IV) within a range that does not impair the effects of the present invention. By providing the [A2] polymer with a structural unit (I) and a structural unit (II-2), the negative radiation-sensitive resin composition (2) is formed with the above-mentioned cured film. Similarly, with the resin composition (1), a hardened film having excellent surface hardness and sufficiently satisfying general characteristics such as sensitivity, development adhesion, chemical resistance, heat resistance, transmittance, and relative dielectric constant can be formed, and Excellent storage stability. In addition, in the negative radiation-sensitive resin composition (2), the hydrogen atom of an alcoholic hydroxyl group is easily detached due to the electron attraction of the fluoroalkyl group in the group represented by the formula (1), and The hydrogen atom of the phenolic hydroxyl group due to the electron attraction of the halogen atom and / or the fluoroalkyl group in the group represented by (2) is easily detached and becomes acidic. As a result, alkali development in the unexposed portion can be reduced. Development residue caused by liquid. The [A2] polymer may have two or more kinds of each structural unit.

[Construction unit (I)]

The structural unit (I) is a structural unit containing at least one selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2).

Since this structural unit (I) is the same as the structural unit (I) in the above-mentioned [A1] polymer, detailed description is omitted.

The content ratio of the structural unit (I) is preferably 5 mol% or more and 90 mol% or less, more preferably 20 mol or more and 80 mol% or less, relative to all the structural units constituting the [A2] polymer. It is more preferably 30 mol% or more and 70 mol% or less. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Construction unit (II-2)]

The structural unit (II-2) is a structural unit containing a crosslinkable group (a2).

Examples of the structural unit (II-2) include the same structural unit as the structural unit exemplified in the aforementioned structural unit (II-1).

The crosslinkable group (a2) is preferably selected from the group consisting of an ethylene oxide group, an oxetanyl group, a cyclic carbonate group, and a (meth) acrylfluorenyl group. At least one. This can further improve the chemical resistance of the formed cured film.

The content ratio of the structural unit (II-2) is preferably 1 mol% or more and 70 mol% or less, and more preferably 5 mol% or more and 50 mols relative to all the structural units constituting the [A2] polymer. % Or less, more preferably 10 mol% or more and 30 mol% or less. When the content ratio of the structural unit (II-2) is within the above range, storage stability and the like can be effectively improved.

[Construction unit (III)]

The structural unit (III) is a structural unit other than the structural unit (I), and is a structural unit derived from a (meth) acrylic acid ester having a hydroxyl group, or a structural unit derived from a compound represented by the following formula (3) . When the [A2] polymer has the structural unit (III), control of alkali developability and suppression of residues can be achieved.

In the formula (3), R ′ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom. R ^L1 to R ^L5 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO-, or -CONH-. p is an integer from 0 to 3. However, at least one of R ^L1 to R ^L5 is a hydroxyl group.

As the alkyl group having 1 to 4 carbon atoms represented by the above-mentioned R ^L1 to R ^L5 , for example, the same group as that exemplified as the alkyl group having 1 to 4 carbon atoms represented by the above-mentioned R ¹ to R ⁴ can be applied. Group.

Examples of the structural unit (III) include structural units represented by the following formulae (III-1) to (III-11).

In the formulae (III-1) to (III-11), R ⁸ is a hydrogen atom, a methyl group, or a trifluoromethyl group. p is defined in the same manner as in the above formula (3). Among them, the structural unit (III) is preferably a structural unit represented by the formulae (III-1), (III-4), and (III-10).

As a monomer compound capable of generating the structural unit (III), Preferably it is 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, more preferably 2-hydroxyethyl methacrylate Ester, 4-hydroxyphenyl methacrylate, α-methyl-p-hydroxystyrene.

The content ratio of the structural unit (III) is preferably 0 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 30 mol% or less, relative to all the structural units constituting the [A2] polymer. It is more preferably 3 mol% or more and 20 mol% or less.

[Construction unit (IV)]

The structural unit (IV) is a structural unit other than the aforementioned structural units (I) to (III). The structural unit (IV) is not particularly limited as long as it is a structural unit other than the aforementioned structural units (I) to (III). By providing the [A2] polymer with a structural unit (IV), the negative radiation-sensitive resin composition (2) can adjust the glass transition temperature of the resin, which can improve alkali developability and melt flowability during thermal curing. And / or mechanical strength and chemical resistance of the hardened film.

Examples of the structural unit (IV) include a structural unit represented by the following formulae (IV-1) to (IV-11).

In the formulae (IV-1) to (IV-11), R ⁹ is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer from 1 to 10. Among these, the structural unit (IV) is preferably a structural unit represented by the formulae (IV-1), (IV-2), (IV-7) to (IV-9), (IV-11) .

Examples of the monomer compound capable of generating the structural unit (IV) include (meth) acrylic acid and (meth) acrylic acid chain alkyl esters. Cyclic alkyl (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, and conjugated dicarboxylic acid Olefin compounds, and structural units such as an unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropiperan skeleton, a piperan skeleton or a skeleton represented by the following formula (4), other unsaturated compounds, and the like.

In the formula (4), R ^M and s are defined in the same manner as in the formulas (IV-1) to (IV-11).

Examples of the (meth) acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, and the like. Isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, and other chain alkyl acrylates such as methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate , Secondary butyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, Methacrylic chain alkyl esters, such as n-stearyl methacrylate.

Examples of the cyclic alkyl (meth) acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, Acrylic tricyclic [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, cyclic alkyl acrylate, etc .; cyclohexyl methacrylate, 2-methyl methacrylate Cyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, Cycloalkyl methacrylate and the like such as isoamyl methacrylate and the like.

Examples of the aryl (meth) acrylate include aryl acrylates such as phenyl acrylate and benzyl acrylate; and aryl methacrylates such as phenyl methacrylate and benzyl methacrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

Examples of the bicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] heptane. -2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tertiary butoxycarbonyl) bicycle [2.2.1] Hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, etc.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. Fluorenimine, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimide-3-maleimide Benzoate, N-succinimide-4-maleimideiminobutyrate, N-succinimideimide-6-maleimideiminohexanoate, N-succinimide Amino-3-maleimidoimidopropionate, N- (9-acridyl) maleimidoimine, and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl- P-hydroxystyrene, etc.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Examples of the unsaturated compound having a tetrahydrofuran skeleton include 2-methacryloxy-propane tetrahydrofurfuryl ester, 3- (meth) acryloxytetrahydrofuran-2-one, and (methyl) ) Tetrahydrofurfuryl acrylate, tetrahydro (meth) acrylate, and the like.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furanyl) -1-penten-3-one, furfuryl (meth) acrylate, and 1-furan- 2-butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furanyl) -2-methyl- 1-hexene-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2- Furyl) -6-methyl-1-hepten-3-one and the like.

Examples of the unsaturated compound containing a tetrahydropiperan skeleton include, for example, (tetrahydropiperan-2-yl) methyl methacrylate and 2,6-dimethyl-8- (tetrahydropiperan-2 -Yloxy) -oct-1-en-3-one, tetrahydropiperan-2-yl methacrylate, 1- (tetrahydropiperan-2-oxy) -butyl-3- Ene -2-ketone, etc.

Examples of the unsaturated compound having a piperan skeleton include 4- (1,4-dioxa-5- pendant oxygen-6-heptenyl) -6-methyl-2-piperan, 4- (1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2-piperan and the like.

Examples of the unsaturated compound having a skeleton represented by the formula (4) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (methyl) Group) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

Examples of the other unsaturated compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, and vinyl acetate.

Among these, as the monomer compound capable of generating the above-mentioned structural unit (IV), a chain alkyl methacrylate; a cyclic alkyl methacrylate; a maleimide compound; and a tetrahydrofuran skeleton , Furan skeleton, tetrahydropiperan skeleton, piperan skeleton, unsaturated compounds of the skeleton represented by the above formula (4); unsaturated aromatic compounds; cyclic alkyl acrylates, from copolymerization reactivity and in alkaline aqueous solution From the viewpoint of solubility, styrene, methacrylic acid, methyl methacrylate, tertiary butyl methacrylate, n-lauryl methacrylate, and tricyclic methacrylate [5.2.1.0 ^{2, 6} ] decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, (methyl ) Tetrahydrofurfuryl acrylate, polyethylene glycol (n = 2 ~ 10) mono (meth) acrylate, 3- (meth) propenyloxytetrahydrofuran-2-one.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, relative to all the structural units constituting the [A2] polymer. It is more preferably 3 mol% or more and 60 mol% or less. When the content ratio of the structural unit (IV) is within the above range, chemical resistance can be effectively improved.

<[A2] Synthesis method of polymer>

The method for synthesizing the [A2] polymer is not particularly limited, but, for example, the same method as the method for synthesizing the [A1] polymer described above can be applied.

The polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) as the [A2] polymer is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. When the Mw of the [A2] polymer is in the above range, the sensitivity and developability of the negative radiation-sensitive resin composition (2) can be further improved. The ratio (Mw / Mn) of Mw of the [A2] polymer to the polystyrene-equivalent number average molecular weight (Mn) obtained by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less. .

<[B] Polymerizable compound>

[B] The polymerizable compound is a compound having an ethylenically unsaturated bond. [B] The polymerizable compound may be used alone or in combination of two or more kinds.

[B] The polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, but examples thereof include ω-carboxy polycaprolactone mono (meth) acrylate and (meth) acrylic acid. Monofunctional (meth) acrylate compounds such as 2- (2'-vinyloxyethoxy) ethyl ester, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (methyl) Acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylic acid Esters, bisphenoxyethanol, di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acrylic acid methacrylate Ester, trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylic acid Ester, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid Modified neopentaerythritol triacrylate, by having a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule and three to five A polyfunctional (meth) acrylate compound and the like obtained by reacting a compound of (meth) acrylic fluorenyloxy groups and the like.

As commercially available products of [B] polymerizable compounds, for example, Aronix M-400, same M-402, same M-405, same M-450, same M-1310, same M-1600, and same M -1960, as M-7100, as M-8030, as M-8060, as M-8100, as M-8530, as M-8560, as M-9050, Aronix TO-1450, as TO-1382 (above, East Asia Synthesis), KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, manufactured by Nippon Kayaku), Viscoat 295, 300, 360, Same as GPT, same as 3PA, same as 400 (above, manufactured by Osaka Organic Chemical Industry), Examples of the urethane acrylate-based compounds include: New Frontier R-1150 (made by Daiichi Kogyo), KAYARAD DPHA-40H, UX-5000 (above, manufactured by Nippon Kayaku), and UN-9000H (Gengami Industries) System), Aronix M-5300, same M-5600, same M-5700, same M-210, same M-220, same M-240, same M-270, same M-6200, same M-305, same M -309, same M-310, same M-315 (above, manufactured by East Asia), KAYARAD HDDA, KAYARAD HX-220, same HX-620, same R-526, same R-167, same R-604, same R -684, same as R-551, same as R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU -2100, MU-4001 (above, made by Nippon Kayaku), Art Resin UN-9000PEP, same as UN-9200A, same as UN-7600, same as UN-333, same as UN-1003, same as UN-1255, and same as UN-6060PTM Same as UN-6060P (above, manufactured by Roots Industrial), SH-500B Viscoat 260, same as 312, same as 335HP (above, manufactured by Osaka Organic Chemical Industry), etc.

[B] The polymerizable compound preferably has at least one carboxyl group in the same molecule. This makes it possible to improve the crosslinkability and reduce the development residue in the unexposed portion. [B] polymerizable compounds having at least one carboxyl group in the same molecule are preferably ω-carboxy polycaprolactone mono (meth) acrylate and succinic acid-modified neopentaerythritol triacrylate.

The content of the [B] polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the [A2] polymer. More preferably, it is 40 mass parts or more and 160 mass parts or less. When the content of the [B] polymerizable compound is in the above range, the negative-type radiation-sensitive resin composition (2) can form a cured film having excellent adhesion and sufficient surface hardness even at a low exposure amount.

<[C] Radiation-sensitive polymerization initiator>

[C] The radiation-sensitive polymerization initiator is a component that generates a reactive species that can initiate the polymerization of the [B] polymerizable compound by sensing radiation. Examples of the [C] radiation-sensitive polymerization initiator include an oxime ester compound, an acetophenone compound, and a biimidazole compound. [C] The radiation-sensitive polymerization initiator may be used alone or in combination of two or more.

Examples of the oxime ester compound include ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-ethyl Amidoxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzylideneoxime)], 1- [9-ethyl-6-benzylidene- 9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole- 3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzyl) -9H-carbazol-3-yl ] -Ethane-1-one oxime-O-benzoate, ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzyl) -9H-carbazole -3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydropiperanylbenzyl) -9H- Carbazol-3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzyl) -9H-carb Azol-3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3 -Dioxolyl) methoxybenzylidene} -9H-carbazol-3-yl] -1- (O-acetamoxime) and other O-fluorenyl oxime compounds and the like. Among these, as the oxime ester compound, ethyl ketone-1- [9-ethyl-6- (2-methylbenzyl) ) -9H-carbazol-3-yl] -1- (O-acetamoxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzyloxime) )], Ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -1- (O- Acetooxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl Fluorenyl} -9H-carbazol-3-yl] -1- (O-acetamoxime).

Examples of the acetophenone compound include an α-amino ketone compound and an α-hydroxy ketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenyl-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylphenylthio) -2- Phenylpropane-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

The acetophenone compound is preferably an α-amino ketone compound, and more preferably 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenyl-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylphenylthio) -2- Phenylpropane-1-one.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrabenzene -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Examples of commercially available products of the [C] radiation-sensitive polymerization initiator include 2-methyl-1- (4-methylphenylthio) -2- Phenylpropane-1-one (IRGACURE 907), 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Porphyrin-4-yl-phenyl) -butane-1-one (IRGACURE 379), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzidine oxime) ] (IRGACURE OXE01), ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamoxime) ( IRGACURE OXE02) (above, manufactured by Ciba Specialty Chemicals) and the like.

The content of the [C] radiation-sensitive polymerization initiator is preferably from 0.1 to 40 parts by mass, and more preferably from 0.5 to 20 parts by mass based on 100 parts by mass of the [A2] polymer. By making the content of the [C] radiation-sensitive polymerization initiator into the above-mentioned range, the negative radiation-sensitive resin composition (2) can be formed to have sufficient surface hardness even at a low exposure amount, and then Sexual hardened film.

Further, the [C] radiation-sensitive polymerization initiator is an oxime ester compound, and the content of the oxime ester compound is preferably 0.1 to 10 parts by mass, more preferably 1 to 100 parts by mass of the [A2] polymer. 5 parts by mass or less. This makes it possible to efficiently form a cured film having sufficient surface hardness and adhesiveness even at a low exposure amount.

<[D] Antioxidant>

[D] Antioxidants are free radicals produced by exposure or heat A component that is decomposed by peroxide or peroxide generated by oxidation to prevent cleavage of the bonds of polymer molecules. [D] As the antioxidant, the antioxidant described in the above-mentioned item of <Resin composition for hardened film formation (1)> can be applied. When the negative radiation-sensitive resin composition (2) contains the [D] antioxidant, the oxidative degradation of the obtained cured film over time can be prevented, and for example, the change in film thickness of the cured film can be suppressed. Moreover, [D] antioxidant can be used individually or in combination of 2 or more types.

The content of the [D] antioxidant is preferably 0 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the [A2] polymer. By making the content of the [D] antioxidant into the above range, it is possible to effectively prevent oxidative degradation of the obtained cured film with time.

<Other optional ingredients>

Examples of other optional components that may be contained in the negative radiation-sensitive resin composition (2) include, in addition to solvents, [E] surfactants, [F] adhesion aids, and the like. For each of the other optional components, those described in the above-mentioned item <Resin composition for hardened film formation (1)> can be applied.

<Method for preparing negative radiation-sensitive resin composition (2)>

The negative-type radiation-sensitive resin composition (2) of the present invention can be prepared by mixing the [A2] polymer with other components as necessary in a predetermined ratio, and it is preferably dissolved in an appropriate solvent. As the solvent used in the preparation of the negative radiation-sensitive resin composition (2), for example, it can be applied to the above-mentioned item "Method for preparing the resin composition (1) for forming a cured film") Exemplary solvents are the same solvents and the like. The prepared negative-type radiation-sensitive resin composition (2) is preferably filtered with a filter having a pore size of about 0.2 μm, for example.

<Method for Forming Hardened Film (2)>

The method (2) of forming a cured film of the present invention has the following steps: (1) using the negative radiation-sensitive resin composition (2), a step of forming a coating film on a substrate (hereinafter, also referred to as "step (B1) ) "), (2) a step of irradiating a part of the coating film with radiation (hereinafter, also referred to as" step (B2) "), and (3) a step of developing the coating film with radiation radiated (hereinafter, also It is called "step (B3)"), and (4) a step of heating the coating film after the development (hereinafter, also referred to as "step (B4)").

Since the negative radiation-sensitive resin composition (2) has the above-mentioned properties, according to the method (2) for forming a cured film of the present invention, heat resistance, chemical resistance, transmittance, relative permittivity, and the like can be sufficiently formed. It has a general characteristic and a hardened film with excellent surface hardness. Hereinafter, each step will be described in detail.

[Step (B1)]

In this step, a coating film is formed on the substrate by using the negative radiation-sensitive resin composition (2). Specifically, the solution of the negative-type radiation-sensitive resin composition (2) is applied to the surface of the substrate, and the solvent is preferably removed by pre-baking to form a coating film. Examples of the substrate include a glass substrate, a silicon wafer, a plastic substrate, and a substrate obtained by forming various metal thin films on the surfaces. Examples of the plastic substrate include polyethylene terephthalate (PET), Resin substrates of plastics such as polybutylene terephthalate (PBT), polyether fluorene, polycarbonate, and polyimide.

As a coating method, for example, a suitable method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be adopted. Among these, as the coating method, a spin coating method, a bar coating method, and a slit die coating method are preferable. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like. For example, it can be set to about 60 ° C. to 130 ° C. for about 30 seconds to about 10 minutes. The film thickness of the formed coating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm as a value after pre-baking.

[Step (B2)]

In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in the step (B1) is irradiated with radiation through a photomask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser and the like. Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include electron beams. Among these radiation rays, ultraviolet rays are preferable, and among ultraviolet rays, radiations including g rays, h rays, and / or i rays are more preferable. The radiation exposure is preferably from 0.1 J / m ² to 10,000 J / m ² .

[Step (B3)]

In this step, the radiation-irradiated coating film is developed. Specifically, for the coating film irradiated with radiation in step (B2), Development is performed with a developing solution to remove the irradiated portion. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and diethylaminoethanol. , Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8 -Diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane and other alkali (basic compounds) aqueous solutions, etc. . In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant to the aqueous solution of the base, or containing a small amount of the negative-type radiation-sensitive resin composition (2 As the developer, alkaline aqueous solutions of various organic solvents are used.

As a developing method, for example, a suitable method such as a liquid coating method, a dipping method, a shaking dipping method, or a shower method can be adopted. The development time differs depending on the composition of the negative radiation-sensitive resin composition (2), and it can be set to, for example, 30 seconds to 120 seconds. Further, it is preferable that after the developing step, the patterned coating film is subjected to a washing treatment by flowing water washing, and then the entire surface is irradiated (post-exposure) with radiation caused by a high-pressure mercury lamp or the like to perform Decomposition treatment of [C] radiation-sensitive polymerization initiator remaining in the coating film. After that, the exposure amount during exposure is preferably 2,000 J / m ² to 5,000 J / m ² .

[Step (B4)]

In this step, the developed coating film is heated. Specifically, a heating device such as a hot plate or an oven that heats the coating film developed in step (B3) is used to heat-treat the coating film ( Post-baking) to harden the coating film. The heating temperature in this step is preferably 200 ° C or lower. A fine pattern can be formed using radiation-sensitive radiation, and heating can be performed at such a low temperature. Therefore, the method (2) for forming a cured film can be preferably used to form an interlayer insulating film on a plastic substrate of a flexible display. And so on. The heating temperature is more preferably 120 ° C to 180 ° C, and still more preferably 120 ° C to 150 ° C. The heating time varies depending on the type of heating equipment, but it can be set to 5 minutes to 40 minutes when heating is performed on a hot plate, and 30 minutes to 80 when heating is performed in an oven. The minute is more preferably 30 minutes or less when the heat treatment is performed on a hot plate, and 60 minutes or less when the heat treatment is performed in an oven. By doing so, a patterned coating film corresponding to a hardened film such as an interlayer insulating film can be formed on the substrate.

<Hardened film (2)>

The cured film (2) of the present invention is formed from the negative radiation-sensitive resin composition (2). The method for forming the cured film (2) is not particularly limited, but it is preferably formed by using the method (2) for forming the cured film described above. Since the hardened film (2) is formed of the negative radiation-sensitive resin composition (2), it has excellent surface hardness and can fully satisfy general characteristics such as chemical resistance, heat resistance, transmittance, and relative dielectric constant. . Since this cured film (2) has the above-mentioned characteristics, it is suitable as, for example, an interlayer insulating film, a spacer, a protective film, a colored pattern for a color filter, etc. of a display element.

<Semiconductor element>

The semiconductor element of the present invention includes the cured film (the above-mentioned cured film) Film (1) or hardened film (2)). This cured film is used, for example, as an interlayer insulating film etc. which insulates between wirings in this semiconductor element. The semiconductor element can be formed by using a known method. Since the semiconductor element is provided with the cured film, it can be applied to electronic devices such as display elements, LEDs, and solar cells.

<Display element>

The display element of the present invention includes the semiconductor element. Since the display element includes a semiconductor element having the cured film, it satisfies the general characteristics required for a display element in practical terms. As this display element, a liquid crystal display element etc. are mentioned, for example. In the above-mentioned liquid crystal display element, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged opposite to each other on the liquid crystal alignment film side via a sealant provided on a peripheral portion of the TFT array substrate. Liquid crystal is filled between the TFT array substrates. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the cured film as an interlayer insulating film.

<Display element>

The display element of the present invention includes the semiconductor element. Since the display element includes a semiconductor element having the cured film, it satisfies the general characteristics required for a display element in practical terms. As this display element, a liquid crystal display element etc. are mentioned, for example. In the above-mentioned liquid crystal display element, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged opposite to each other on the liquid crystal alignment film side via a sealant provided on a peripheral portion of the TFT array substrate. Liquid crystal is filled between the TFT array substrates. The TFT array substrate has a layered arrangement The wiring between the wirings is insulated by using the cured film as an interlayer insulating film.

<Positive radiation-sensitive resin composition>

The positive-type radiation-sensitive resin composition of the present invention contains a [A3] polymer and a [G] acid generator. The positive-type radiation-sensitive resin composition may contain a [H] solvent as a suitable component. Furthermore, this positive-type radiation-sensitive resin composition may contain other optional components in the range which does not impair the effect of this invention. Each component is described in detail below.

<[A3] polymer>

[A3] The polymer is a polymer having structural units (I) and (II-3). Moreover, [A3] polymer may have a structural unit (III) and a structural unit (IV) in the range which does not impair the effect of this invention. The [A3] polymer may have two or more kinds of each structural unit.

[Construction unit (I)]

The structural unit (I) is a structural unit selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2). The [A3] polymer has a structural unit (I) and a structural unit (II-3) described later, so that the positive-type radiation-sensitive resin composition can form a cured film as follows. The cured film has a well-maintained surface. In addition to being excellent in hardness and storage stability, general characteristics such as sensitivity, development adhesion, heat resistance, chemical resistance, transmittance, and relative permittivity can be fully satisfied. This is presumably because the hydroxyl group in the group represented by the formula (1) and / or (2) contained in the structural unit (I) and the cyclic group contained in the structural unit (II-3) described later. The ether and / or cyclic carbonate reaction can maintain the surface hardness of the cured film by forming a strong cross-linked structure. The reaction is not easy to proceed at normal temperature, and as a result, thickening during storage can be suppressed and good storage stability can be obtained.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² is a fluoroalkyl group having 1 to 4 carbon atoms.

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and secondary butyl. , Tertiary butyl, etc.

The fluoroalkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ described above is a group in which a part or all of the hydrogen atoms in the alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. As the alkyl group having 1 to 4 carbon atoms, for example, the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ can be applied.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The R ¹ to R ^{4 are} preferably a fluoroalkyl group having 1 to 4 carbon atoms and a halogen atom. The fluoroalkyl group having 1 to 4 carbon atoms is more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and further more preferably a trifluoromethyl group. The halogen atom is more preferably a fluorine atom.

As a structural unit (I) containing a group represented by the said Formula (1), the structural unit represented by following formula (1a) and (1b) is preferable.

In the formulae (1a) and (1b), R is each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ¹ and R ^{2 are} defined in the same manner as in the above formula (1). R ⁵ and R ⁶ are each independently a (n + 1) -valent organic group. n are each independently an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ and R ² may be the same or different.

Examples of the (n + 1) -valent organic group represented by R ⁵ and R ⁶ include (n + 1) -valent chain hydrocarbon groups having 1 to 20 carbon atoms, and ((1 + 1) -valent hydrocarbon groups having 3 to 20 carbon atoms. (n + 1) -valent alicyclic hydrocarbon group, or (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a chain-like hydrocarbon group having 1 to 20 carbon atoms, 3 to 20 carbon atoms And two or more (n + 1) -valent groups among alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms. However, some or all of the hydrogen atoms possessed by these groups may be substituted.

Examples of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms include a group in which n hydrogen atoms are removed from a linear or branched alkyl group having 1 to 20 carbon atoms. Mission etc.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, and 1 -Methylpropyl, tertiary butyl, etc.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a group in which n hydrogen atoms are removed from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. .

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like.

Examples of the (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms include a group in which n hydrogen atoms are removed from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Among these, as R ⁵ , a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group in which these groups are combined are more preferable. R ⁵ includes ethylene, 1,2-propyl, 2 Hydrocarbyl group of 2,5-subordinyl, and 2,6-subordinyl. In addition, as R ⁶ , a divalent aromatic hydrocarbon group is preferable, and a phenylene group is more preferable.

As a structural unit (I) containing a group represented by the said Formula (2), the structural unit represented by following formula (2a) and (2b) is preferable.

In the formulae (2a) and (2b), R is defined in the same manner as the formulae (1a) and (1b). R ³ and R ^{4 are} defined in the same manner as in the above formula (2).

Examples of the structural unit (I) include structural units represented by the following formulae (I-1) to (I-15).

In the above formula, R and the above formulas (1a), (1b), (2a), and (2b) Same definition. Among these, as the structural unit (I), the structural units represented by the formulae (I-1) to (I-6), (I-9), and (I-11) to (I-13) are preferred. From the viewpoint of alkali developability and thermosetting properties, the structural units represented by the formulae (I-1) to (I-6) are more preferred.

The content ratio of the structural unit (I) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol or more and 80 mol% or less, with respect to all the structural units constituting the [A3] polymer. It is more preferably 30 mol% or more and 70 mol% or less. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Construction unit (II-3)]

The structural unit (II-3) is a structural unit including a cyclic ether structure or a cyclic carbonate structure.

Examples of the cyclic ether structure include an ethylene oxide structure (1,2-epoxy structure), an oxetane structure (1,3-epoxy structure), and a tetrahydrofuran structure.

As the structural unit (II-3), for example, as a structure including an ethylene oxide structure, a structural unit represented by the following formulae (II "-1) to (II" -5) can be cited; Examples of the butane structure include the structural units represented by the following formulae (II "-6) to (II" -9); and those containing the tetrahydrofuran structure include the following formulae (II "-10) and (II) The structural unit and the like represented by "-11); and those containing a cyclic carbonate structure include the structural unit and the like represented by the following formulae (II" -12) to (II "-16).

In the formulae (II "-1) to (II" -16), R ⁷ is a hydrogen atom, a methyl group, or a trifluoromethyl group. Among these, as the structural unit (II-3), from the viewpoint of crosslinkability and chemical resistance, the formulae (II "-1) to (II" -9) and (II "- 12) The structural units represented by (II "-16) are more preferably the structural units represented by formulae (II" -1) to (II "-9), and further more preferably by formula (II" -1) ~ The structural unit represented by (II "-5) is particularly preferably a structural unit represented by formulae (II" -1) to (II "-3).

The content ratio of the structural unit (II-3) is preferably 1 mol% or more and 70 mol% or less, and more preferably 5 mol% or more and 50 mols relative to all the structural units constituting the [A3] polymer. % Or less, more preferably 10 mol% or more and 30 mol% or less. When the content ratio of the structural unit (II-3) is within the above range, storage stability and the like can be effectively improved.

The structural unit (II-3) includes a cyclic ether structure, and the cyclic ether structure is preferably at least any one of an ethylene oxide structure and an oxetane structure. By making the said structural unit (II-3) have the said structure, crosslinkability can be improved, and as a result, this positive radiation sensitive resin composition can improve surface hardness, heat resistance, etc.

[Construction unit (III)]

The structural unit (III) is a structural unit derived from a (meth) acrylic acid ester having a hydroxyl group, or a structural unit derived from a compound represented by the following formula (3). When the [A3] polymer has the structural unit (III), it is possible to control the alkali developability and suppress the residue.

In the formula (3), R ′ is a hydrogen atom or a C 1-4 alkyl group which may be substituted with a fluorine atom. R ^L1 to R ^L5 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO-, or -CONH-. p is an integer from 0 to 3. However, at least one of R ^L1 to R ^L5 is a hydroxyl group.

As the alkyl group having 1 to 4 carbon atoms represented by the above-mentioned R ^L1 to R ^L5 , for example, the same group as that exemplified as the alkyl group having 1 to 4 carbon atoms represented by the above-mentioned R ¹ to R ⁴ can be applied. Group.

Examples of the structural unit (III) include structural units represented by the following formulae (III-1) to (III-11).

In the formulae (III-1) to (III-11), R ⁸ is a hydrogen atom, a methyl group, or a trifluoromethyl group. p is defined in the same manner as in the above formula (3). Among these, the structural unit (III) is preferably a structural unit represented by the formula (III-1), (III-4), and (III-10).

As the monomer compound capable of generating the structural unit (III), 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p Hydroxystyrene is more preferably 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, and α-methyl-p-hydroxystyrene.

The content ratio of the structural unit (III) is preferably 0 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 30 mol% or less, relative to all the structural units constituting the [A3] polymer. It is more preferably 3 mol% or less and 20 mol% or less.

[Construction unit (IV)]

The structural unit (IV) is a structural unit other than the aforementioned structural units (I) to (III). The structural unit (IV) is not particularly limited as long as it is a structural unit other than the aforementioned structural units (I) to (III). By having the [A3] polymer having a structural unit (IV), the glass transition temperature of the resin can be adjusted, and alkali developability, melt fluidity during thermal curing, or mechanical strength and chemical resistance of the cured film can be improved, respectively.

Examples of the structural unit (IV) include structural units represented by the following formulae (IV-1) to (IV-11).

In the formulae (IV-1) to (IV-11), R ⁹ is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer from 1 to 10. Among these, the structural unit (IV) is preferably a structural unit represented by the formulae (IV-1), (IV-2), (IV-7) to (IV-9), (IV-11) .

Examples of the monomer compound capable of generating the structural unit (IV) include (meth) acrylic acid, (meth) acrylic chain alkyl esters, (meth) acrylic cyclic alkyl esters, and (meth) Aryl acrylate, not saturated And dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds and conjugated diene compounds, and having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropiperan skeleton, a piperan skeleton, or Structural units such as unsaturated compounds of the skeleton represented by formula (4), other unsaturated compounds, and the like.

In the formula (4), R ^M and s are defined in the same manner as in the formulas (IV-1) to (IV-11).

Examples of the (meth) acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, and the like. Isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, and other chain alkyl acrylates such as methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate , Secondary butyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, Methacrylic chain alkyl esters, such as n-stearyl methacrylate.

Examples of the cyclic alkyl (meth) acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, Acrylic tricyclic [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, cyclic alkyl acrylate, etc., cyclohexyl methacrylate, 2-methyl methacrylate Cyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate , Cyclic alkyl methacrylate, etc. such as isoamyl methacrylate.

Examples of the aryl (meth) acrylate include aryl acrylates such as phenyl acrylate and benzyl acrylate, and aryl methacrylates such as phenyl methacrylate and benzyl methacrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

Examples of the bicyclic unsaturated compound include bicyclo [2.2.1] heptane-2-ene, 5-methylbicyclo [2.2.1] heptane-2-ene, and 5-ethylbicyclo [2.2.1] ] Heptane-2-ene, 5-methoxybicyclo [2.2.1] heptane-2-ene, 5-ethoxybicyclo [2.2.1] heptane-2-ene, 5,6-dimethyl Oxybicyclo [2.2.1] heptane-2-ene, 5,6-diethoxybicyclo [2.2.1] heptane-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] Heptane-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] heptane-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] heptane-2-ene, 5,6- Bis (tertiary butoxycarbonyl) bicyclo [2.2.1] heptane-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] heptane-2-ene, 5- ( 2'-hydroxyethyl) bicyclo [2.2.1] heptane-2-ene, 5,6-dihydroxybicyclo [2.2.1] heptane-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] Heptane-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] heptane-2-ene, 5-hydroxy-5-methylbicyclo [2.2. 1] heptane-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] heptane-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] heptane-2 -Ene and the like.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N- (4-hydroxyphenyl). ) Maleimide, N- (4-hydroxybenzyl) male Ammonium imine, N-succinimide imino-3-maleimide iminobenzoate, N-succinimide imino-4-maleimide iminobutyrate, N-succinimide Amine-6-maleimidoiminohexanoate, N-succinimidoimido-3-maleimidoiminopropionate, N- (9-acridyl) maleimidoimine, etc. .

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p. Hydroxystyrene, etc.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofuran (meth) acrylate, 2-methacryloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloxy tetrahydrofuran. -2-one, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furanyl) -1-penten-3-one, furfuryl (meth) acrylate, and 1-furan-2 -Butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furanyl) -2-methyl-1 -Hexen-3-one, 6-furan-2-yl-hexyl-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furan Group) -6-methyl-1-hepten-3-one and the like.

Examples of the unsaturated compound containing a tetrahydropiperan skeleton include, for example, (tetrahydropiperan-2-yl) methyl methacrylate and 2,6-dimethyl-8- (tetrahydropiperan-2- (Oxy))-octyl-1-en-3-one, tetrahydropiperan-2-yl methacrylate, 1- (tetrahydropiperan-2-oxy) -butyl-3- En-2-ones, etc.

Examples of the unsaturated compound having a piperan skeleton include 4- (1,4-dioxa-5- pendant oxygen-6-heptenyl) -6-methyl-2-piperan, 4- ( 1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2-piperan and the like.

Examples of the other unsaturated compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, and vinyl acetate.

Among them, as the monomer compound capable of generating the structural unit (IV), a chain alkyl methacrylate, a cyclic alkyl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, Furan skeleton, tetrahydropiperan skeleton, piperan skeleton, unsaturated compound of the skeleton represented by the above formula (4), unsaturated aromatic compound, cyclic alkyl acrylate, from copolymerization reactivity and dissolution in alkali aqueous solution From the viewpoint of performance, styrene, methacrylic acid, methyl methacrylate, tertiary butyl methacrylate, n-lauryl methacrylate, and tricyclic methacrylate are more preferable [5.2.1.0 ^2,6 ] Decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, (meth) acrylic acid Tetrahydrofurfuryl ester, polyethylene glycol (n = 2 ~ 10) mono (meth) acrylate, 3- (meth) propenyloxytetrahydrofuran-2-one.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, relative to all the structural units constituting the [A3] polymer. It is more preferably 3 mol% or more and 60 mol% or less. When the content ratio of the structural unit (IV) is within the above range, chemical resistance can be effectively improved.

<[A3] Polymer Synthesis Method>

[A3] The polymer can be produced, for example, by using a radical initiator to polymerize a monomer corresponding to a predetermined structural unit in an appropriate solvent. For example, it is preferable to synthesize by a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to polymerize it, and a solution containing the monomer and A method for polymerizing a solution in which a solution containing a radical initiator is individually dropped into a solution containing a reaction solvent or a monomer, and a plurality of solutions containing respective monomers and a solution containing a radical initiator are individually dropped A method such as a method of adding it to a solution containing a reaction solvent or a monomer to polymerize it.

The reaction temperature in these methods may be appropriately determined depending on the type of the initiator. It is usually 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, and more preferably 50 ° C to 140 ° C. The dropping time varies depending on the conditions such as the reaction temperature, the type of the initiator, and the monomer to be reacted, but it is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. . In addition, the total reaction time including the dropping time is different from the dropping time depending on conditions, but it is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.

Examples of the radical initiator used in the polymerization include azobisisobutyronitrile (AIBN) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). , 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2- Methylpropionitrile) and the like. These initiators can be used alone or in combination of two or more.

The polymerization solvent is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibitory effect, a mercapto compound having a chain transfer effect, and the like), and is not limited as long as it is a solvent that can dissolve the monomer. Examples of the polymerization solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amidine-based solvents, ester / lactone-based solvents, and nitrile-based solvents. These solvents may be used alone or in combination of two or more.

The polymer obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after the polymerization reaction is terminated, the polymerization solution is put into a reprecipitation solvent, and the target polymer is recovered as a powder. As a reprecipitation solvent, alcohols, alkanes, etc. can be used individually or in mixture of 2 or more types. In addition to the reprecipitation method, the polymer can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.

In the polymerization reaction for producing the [A3] polymer, a molecular weight modifier can be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, and mercapto group. Thiols such as acetic acid; xanthates such as dimethyl xanthate sulfide, diisopropyl xanthate disulfide; terpineolene, α-methylstyrene dimers, etc.

[A3] The polystyrene-equivalent weight average molecular weight (Mw) of the polymer obtained by gel permeation chromatography (GPC) is not particularly limited, but it is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. When the Mw of the [A3] polymer is within the above range, the sensitivity and developability of the positive-type radiation-sensitive resin composition can be improved.

The ratio (Mw / Mn) of the Mw of the [A3] polymer to the polystyrene-equivalent number average molecular weight (Mn) obtained by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less.

<[G] acid generator>

[G] The acid generator generates an acid by irradiation or heating of a ray. This positive-type radiation-sensitive resin composition has a positive-type radiation-sensitive property by removing the exposed portion of the radiation by a development step by containing a [G] acid generator, and by heating in a subsequent heating step. The generated acid functions as a cross-linking catalyst and promotes a cross-linking reaction, and can form a cured film having high heat resistance and surface hardness. The content form of the [G] acid generator in the positive-type radiation-sensitive resin composition may be the form of a compound described below (hereinafter, this form is also referred to as "[G] acid generator"), or It may be in the form of being incorporated as a part of the polymer, or both. The radiation is a concept including visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays.

Examples of the [G] acid generator include an oxime sulfonate compound, a fluorenimine compound, and a quinonediazide compound. Moreover, these [G] acid generators can be used individually or in combination of 2 or more types.

The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (5).

In the formula (5), R ^a is an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, some or all of the hydrogen atoms of these alkyl groups, alicyclic groups, and aryl groups may be substituted by a substituent.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^a include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl. Base etc. Among these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred.

Carbon atoms, an alicyclic group having 3 to 20, as represented by the above R ^a, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the substituent which the alkyl group and the alicyclic group may have include, for example, an alkoxy group having 1 to 10 carbon atoms, and an alicyclic group having 1 to 10 carbon atoms.

Examples of the alkoxy group having 1 to 10 carbon atoms as the substituent include a methoxy group and an ethoxy group.

As the alicyclic group having 1 to 10 carbon atoms as the substituent, for example, an alicyclic group having 1 to 10 carbon atoms in the alicyclic group having 3 to 20 carbon atoms represented by the above-mentioned R ^a can be applied.式 基。 Formula base.

Carbon atoms, an aryl group having 6 to 20 as represented by the above R ^a, for example, a phenyl, tolyl, xylyl, naphthyl, anthryl and so on. Among these, an aryl group having 6 to 11 carbon atoms is preferred, and a phenyl group and a naphthyl group are more preferred.

Examples of the substituent which may be contained in the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and the like.

Examples of the alkyl group having 1 to 5 carbon atoms as the substituent include a methyl group and an ethyl group.

Examples of the alkoxy group having 1 to 5 carbon atoms as the substituent include a methoxy group and an ethoxy group.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As a compound containing the oxime sulfonate group represented by the said Formula (5), the oxime sulfonate compound represented by the following formula (5-1) and (5-2) is preferable.

In the formulae (5-1) and (5-2), R ^a is defined in the same manner as in the formula (5). X is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. m is an integer from 0 to 3. When m is 2 or 3, a plurality of X may be the same or different.

As the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, and a halogen atom represented by X, for example, the same groups as the respective groups exemplified as the substituents described above can be applied. . Among these, the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkoxy group is preferably a linear chain having 1 to 4 carbon atoms. Or a branched alkoxy group, as said halogen atom, a chlorine atom or a fluorine atom is preferable. In addition, m is preferably 0 or 1. In particular, in the formula (5-1), a compound in which m is 1, X is a methyl group, and a substitution position of X is an ortho position is preferred.

Examples of the oxime sulfonate compound represented by the formula (5) include the following formulae (5-1-i) to (5-1-iv), and (5-2-i) and (5- 2-ii) Compounds and the like.

Examples of the fluorenimine compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, and N- (4- Methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) Naphthalenedicarboxyfluorene imine (trifluoromethanesulfonic acid-1,8-naphthalenedimethylamine imine), N- (Camphorsulfonyloxy) naphthalenedicarboxylic acid imine, N- (4-methylbenzene Sulfofluorenyloxy) naphthalenedicarboxyfluorenimine, N- (phenylsulfonyloxy) naphthalenedicarboxyfluorenimine, N- (2-trifluoromethylphenylsulfonyloxy) naphthalene Dicarboxyfluorenimine, N- (4-fluorophenylsulfonyloxy) naphthalenedicarboxyfluorenimine, N- (pentafluoroethylsulfonyloxy) naphthalenedicarboxyfluorenimine, N- ( Heptafluoropropylsulfonyloxy) naphthalenedicarboxyfluoreneimine, N- (nonafluorobutylsulfonyloxy) naphthalenedicarboxyfluoreneimine, N- (ethylsulfonyloxy) naphthalenediamine Carboximinoimide, N- (propylsulfonyloxy) naphthalenedicarboxyfluoreneimine, N- (butylsulfonyloxy) naphthalenedicarboxyfluoreneimine, N- (pentylsulfonyloxy) ) Naphthalene dicarboxyfluorenimine, N- (hexylsulfonyl) (Oxy) naphthalenedicarboxyfluorenimine, N- (heptylsulfonyloxy) naphthalenedicarboxyfluorenimine, N- (octylsulfonyloxy) naphthalenedicarboxyfluorenimine, N- (nonyl Sulfofluorenyloxy) naphthalenedicarboxyfluorenimine and the like.

As the quinonediazide compound, for example, a phenolic compound or an alcoholic compound (hereinafter, also referred to as a "mother core") and 1,2-naphthoquinonediazidesulfonium halide or 1,2-naphthalene can be used. Condensate of quinonediazidesulfonamide.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and others Other mother cores.

As specific examples of the above-mentioned mother core, for example, as the trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like; as tetrahydroxy Benzophenones include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrakis Hydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone Etc .; as pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, etc .; as hexahydroxybenzophenone, 2,4,6,3' , 4 ', 5'-hexahydroxybenzophenone, 3,4,5,3', 4 ', 5'-hexahydroxybenzophenone, etc .; as (polyhydroxyphenyl) alkane, bis ( 2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) ethane, bis (2,3 , 4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tri (2,5-dimethyl-4-hydroxyphenyl) ) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol, bis (2 , 5-dimethyl-4-hydroxyl Phenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobisindene-5,6,7,5', 6 ', 7'- Hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan, etc .; as other mother cores, 2-methyl-2- (2,4-dihydroxybenzene ) -4- (4-hydroxyphenyl) -7-hydroxychromogen, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6 -Dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl ) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

Among these, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 '-[ 1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol.

As the 1,2-naphthoquinonediazidesulfofluorene halide, 1,2-naphthoquinonediazidesulfofluorenyl chloride is preferred, and 1,2-naphthoquinonediazide-4- Sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride are further preferably 1,2-naphthoquinonediazide-5-sulfonyl chloride.

As said 1,2-naphthoquinonediazidesulfonamide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide is preferable.

In the condensation reaction of the above-mentioned phenolic compound or alcoholic compound (mother core) with 1,2-naphthoquinonediazidesulfosulfonyl halide, the number of OH groups in the phenolic compound or alcoholic compound may be The equivalent of 1,2-naphthoquinonediazidesulfonyl halide is preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol%. The condensation reaction can be carried out by a known method.

The content of the [G] acid generator is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 100 parts by mass of the [A3] polymer. At least 40 parts by mass. When the content of the [G] acid generator is in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkali aqueous solution to be a developing solution is large. As a result, the patterning performance becomes good, and the obtained The chemical resistance of the cured film is also improved.

<[H] solvent>

[H] Solvent can use [A3] polymer, [G] acid generator, and And a solvent which optionally dissolves an arbitrary component and does not react with each component. The [H] solvent may be used alone or in combination of two or more.

Examples of the [H] solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amidine-based solvents, ester-based solvents, and hydrocarbon-based solvents.

Examples of the alcohol-based solvent include, for example, a monohydric alcohol-based solvent, including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, Isoamyl alcohol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol , Secondary heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, secondary Undecyl alcohol, trimethylnonanol, secondary tetradecanol, secondary heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol Alcohols, benzyl alcohol, diacetone alcohol, and the like; examples of the polyhydric alcohol solvent include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, and 2-methyl-2 , 4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, triethylene glycol Propylene glycol and the like; Examples of the polyol-based partial ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol. Alcohol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether , Diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethylene glycol. Diethyl ether, tetrahydrofuran, etc.

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, and ethyl n-butyl. Ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione , Acetone acetone, acetophenone, etc.

Examples of the amidamine-based solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, and N, N-diethylformamidine. Amine, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropylamine, N-methylpyrrolidone, and the like.

Examples of the ester-based solvent include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, n-pentyl acetate, and diacetate. Grade amyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl ester, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetic acid Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propyl acetate Glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, propylene N-butyl acid, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate , Dimethyl phthalate, diethyl phthalate, etc.

Examples of the hydrocarbon-based solvent include, as examples of the aliphatic hydrocarbon-based solvent, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, and 2,2,4-trimethylpentane. , N-octane, isooctane, cyclohexane, methylcyclohexane, etc .; Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, Methyl ethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene and the like.

In addition, the [H] solvent may contain a high boiling point solvent such as hexanoic acid, caprylic acid, ethylene carbonate, propylene carbonate, etc. together with the above-mentioned solvent.

<Other optional ingredients>

Examples of other optional components that may be contained in the positive-type radiation-sensitive resin composition include, for example, a cyclic ether compound (hereinafter, also referred to as "compound X"), an antioxidant, and an interface other than the [A3] polymer. Active agents, adhesion aids, etc. In the positive-type radiation-sensitive resin composition, each of the above components may be used alone, or two or more of them may be used in combination.

[Compound X]

Compound X is a cyclic ether compound other than the [A3] polymer. Specifically, it is a compound having a thermally reactive group such as an ethylene oxide group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). When the positive-type radiation-sensitive resin composition contains the compound X, the heat resistance and surface hardness of the obtained cured film can be improved. The compound X is preferably a compound having two or more ethylene oxide groups or oxetanyl groups in the molecule.

Examples of the compound X having two or more ethylene oxide groups in the molecule include, for example, bisphenol type diglycidyl ethers, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, etc .; polyglycidyl ethers as polyols Examples include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc .; polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol Polyglycidyl ethers of alcohols; phenol novolac epoxy resins; cresol novolac epoxy resins; polyphenol epoxy resins; diglycidyl esters of aliphatic long-chain dibasic acids; shrinkage of higher fatty acids Glycerides; aliphatic polyglycidyl ethers; Epoxidized soybean oil, epoxidized linseed oil, etc.

As a commercially available product of the compound X having two or more ethylene oxide groups in the molecule, for example, as the bisphenol A type epoxy resin, Epikote 1001, the same 1002, the same 1003, the same 1004, the same 1007, the same 1009, same as 1010, same as 828 (above, manufactured by Japan Epoxy Resins), etc. As the bisphenol F-type epoxy resin, Epikote 807 (made by Japan Epoxy Resins), etc., and as the phenol novolak epoxy resin, Epikote can be cited 152, same as 154, same as 157S65 (above, made by Japan Epoxy Resins), EPPN201, same as 202 (above, made by Nippon Kayaku), etc. As the cresol novolac type epoxy resin, EOCN102, the same 103S, the same 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku), Epikote 180S75 (made by Japan Epoxy Resins), etc. As the polyphenol epoxy resin, Epikote 1032H60, the same as XY-4000 (above, made by Japan Epoxy Resins), etc. Examples of the cyclic aliphatic epoxy resin include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 ( Above, made by UCC), Shodyne 509 (made by Showa Denko), EPICLO N 200, same as 400 (above, manufactured by Daikoku Ink), Epikote 871, same as 872 (above, manufactured by Japan Epoxy Resins), ED-5661, same as 5662 (above, manufactured by Celanese Coating), etc., as aliphatic polyglycidyl Examples of the ether include Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epioru TMP (manufactured by Nihon Grease), and the like.

Examples of the compound X having two or more oxetanyl groups in the molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [ 1-ethyl- (3-oxetanyl) methyl] ether (alias: bis (3-ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetan Butyl) -5-oxa-nonane, 3,3 '-[1,3- (2-methylene) propanediylbis (oxymethylene)] bis- (3-ethyloxane Butane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanyl methyl) ether, triethyl Diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3 -Oxetanylmethoxy) butane, xylenedioxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, neopentyltriol 3-ethyl-3-oxetanylmethyl) ether, neopentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxo Heterocyclobutylmethyl) ether, dineopentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dineopentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether , Dipentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, Caprolactone modified dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, bis (trimethylolpropane) tetrakis (3-ethyl-3-oxetanylmethyl) Ether, EO modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, EO modified Hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogen Bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanyl methyl) ether, and the like.

Among these, as the compound X having two or more oxetanyl groups in the molecule, di [1-ethyl- (3-oxetanyl) methyl] ether, 1,4- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.

The content of the compound X is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the [A3] polymer. Mass parts or less. When the content of the compound X is in the above range, sensitivity, heat resistance, and the like can be improved.

[Antioxidants]

The antioxidant is a component that can decompose free radicals generated by exposure or heating or peroxides generated by oxidation to prevent cleavage of the bonds of polymer molecules. As a result, the obtained cured film can be prevented from undergoing oxidative degradation with time, and for example, changes in the film thickness of the cured film can be suppressed.

Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among these, a compound having a hindered phenol structure is preferred as the antioxidant.

Examples of the compound having a hindered phenol structure include neopentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylene glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionate, tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tri ( 3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tertiary-butyl-4 -Hydroxyphenylpropanamine), 3,3 ', 3', 5 ', 5'-Hexa-tertiary-butyl-a, a', a '-(mesitylmethyl-2,4,6 -Triyl) tri (p-cresol), 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, elongation Ethylbis (oxoethylene) bis [3- (5-tertiarybutyl-4-hydroxy-m-tolyl) propionate, hexamethylenebis [3- (3,5-di-tri Butyl-4-hydroxyphenyl) propionate], 1,3,5-tri [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3 , 5-three -2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tertiary-butyl-4- (4,6-bis (octylthio) -1,3,5-tris 2-ylamino) phenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, 2,6- Di-tertiary butyl-4-cresol and the like.

As commercially available products of the compound having a hindered phenol structure, for example, Adekastab AO-20, the same AO-30, the same AO-40, the same AO-50, the same AO-60, the same AO-70, and the same AO- 80. Same as AO-330 (above, made by ADEKA), sumilizerGM, same GS, same MDP-S, same BBM-S, same WX-R, same as GA-80 (above, made by Sumitomo Chemical), IRGANOX1010, same as 1035, Same as 1076, same as 1098, same as 1135, same as 1330, same as 1726, same as 1425WL, same as 1520L, same as 245, same as 259, same as 3114, same as 565, IRGAMOD295 (above, made by BASF), Yoshinox BHT, same BB, same as 2246G, Same as 425, 250, 930, SS, TT, 917, 314 (above, manufactured by API Corporation), and the like.

Among these, as the compound having a hindered phenol structure, neopentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-trimethyl-2,4,6-tri (3,5-di-tertiarybutyl-4-hydroxybenzyl ) Benzene, 2,6-di-tertiary-butyl-4-cresol.

The content of the antioxidant is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass based on 100 parts by mass of the [A3] polymer.

[Interactive agent]

A surfactant is a component which improves the film formation property of this positive-type radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, a polysiloxane-based surfactant, and other surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain, and examples thereof include 1,1,2,2- Tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di ( 1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol bis (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1, 1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol bis (1,1,2,2-tetrafluoro-n-butyl) ether, sodium perfluoron-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane or fluoroalkylbenzene Sodium sulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxidation Vinyl ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, fluoroalkyl carboxylate, and the like.

Examples of commercially available products of the above-mentioned fluorine-based surfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), Megafac F142D, F172, F173, F183, F178, F191, Same as F471, Same as F476 (above, manufactured by Daikoku Ink Chemical Industry), Fluorad FC-170C, Same -171, Same -430, Same -431 (above, made by Sumitomo 3M), Surflon S-112, Same -113, Same -131, same -141, same -145, same -382, Surflon SC-101, same -102, same -103, same -104, same -105, same -106 (above, made by Asahi Glass), Eftop EF301, same 303, same as 352 (above, new Akita Kasei), Ftergent FT-100, same -110, same -140A, same -150, same -250, same -251, same -300, same -310, same -400S, FTX-218, same as -251 (above, made by NEOS), etc.

Examples of commercially available products of the aforementioned polysiloxane surfactants include Toray silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SH-193. SZ-6032, same as SF-8428, same as DC-57, same as DC-190 (above, manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF- 4452 (above, manufactured by GE Toshiba Silicone), organic silicone polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene-n-octyl Polyphenylene oxide, polyoxyethylene-n-nonylphenyl ether, etc., polyoxyethylene aryl ethers, polyoxyethylene dilaurate, polyoxyethylene distearate, etc. Non-ionic surfactant.

Examples of commercially available products of the other surfactants mentioned above include (meth) acrylic copolymer Polyflo No. 57 and No. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).

The content of the surfactant is preferably from 0.01 to 3 parts by mass, more preferably from 0.05 to 1 part by mass, based on 100 parts by mass of the [A3] polymer. When the content of the surfactant is in the above range, the film-forming properties can be effectively improved.

[Adhesion aid]

The adhesion auxiliary agent is a component that improves the adhesion between the obtained cured film and the substrate. As said adhesion auxiliary agent, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, and an ethylene oxide group, is preferable.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane. , Γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The content of the adhesion assistant is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the [A3] polymer. When the usage-amount of an adhesion adjuvant exceeds 20 mass parts, there exists a tendency for the development residue to occur easily.

<Method for preparing a positive radiation-sensitive resin composition>

The positive-type radiation-sensitive resin composition of the present invention can assist the [A3] polymer, the [G] acid generator, the [H] solvent, an antioxidant, a surfactant, and an adhesion assistant in a predetermined ratio. Any components such as agents are mixed and prepared. The prepared positive-type radiation-sensitive resin composition is preferably filtered with a filter having a pore size of about 0.5 μm, for example.

<Method for Forming Hardened Film (3)>

The method (3) of forming a cured film of the present invention has the following steps: (1) a step of forming a coating film on a substrate using the positive-type radiation-sensitive resin composition; (2) irradiating a part of the coating film with radiation Steps; (3) a step of developing the radiation-coated coating film; and (4) a step of heating the developed coating film.

Since the positive radiation-sensitive resin composition has the above-mentioned properties, according to the method (3) for forming a cured film of the present invention, it is possible to form a resin having a good surface hardness and sufficiently satisfying the development adhesion, heat resistance, and chemical resistance. Hardened film with general properties such as transmittance and relative permittivity. Hereinafter, each step will be described in detail.

[Step (C1)]

In this step, a coating film is formed on the substrate by using the positive radiation-sensitive resin composition. Specifically, the solution of the positive radiation-sensitive resin composition is applied on the surface of the substrate, and it is preferable to perform pre-baking to remove the solvent to form a coating film of the radiation-sensitive resin composition. Examples of the substrate include a glass substrate, a silicon wafer, a plastic substrate, and a substrate obtained by forming various metal thin films on the surfaces thereof. Examples of the plastic substrate include plastics including polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether fluorene, polycarbonate, and polyimide. Resin substrate.

As a coating method, for example, a suitable method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be adopted. Of these, spin coating is preferred As the coating method, a bar coating method, a slot die coating method, or the like is used. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like. For example, it can be set to about 60 ° C. to 130 ° C. for about 30 seconds to about 10 minutes. The film thickness of the formed coating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm as a value after pre-baking.

[Step (C2)]

In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in step (C1) is irradiated with radiation through a photomask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser and the like. Examples of the X-ray include synchronous radiation and the like. Examples of the charged particle beam include electron beams. Among these radiation rays, ultraviolet rays are preferable, and among ultraviolet rays, rays including g rays, h rays, and / or i rays are more preferable. The radiation exposure is preferably from 0.1 J / m ² to 10,000 J / m ² .

[Step (C3)]

In this step, the radiation-irradiated coating film is developed. Specifically, for the coating film irradiated with the radiation in step (C2), development is performed with a developing solution to remove the irradiated portion of the radiation. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and diamine. N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethyl Ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5 -An aqueous solution of a base (basic compound) such as nonane. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant to the aqueous solution of the base, or a small amount of the positive-type radiation-sensitive resin composition that can be dissolved may be used. Aqueous alkaline solutions of various organic solvents are used as the developing solution.

As a developing method, for example, a suitable method such as a liquid coating method, a dipping method, a shaking dipping method, or a shower method can be adopted. The development time varies depending on the composition of the positive radiation-sensitive resin composition, and it can be set to, for example, 30 seconds to 120 seconds. Further, it is preferable that after the developing step, the patterned coating film is subjected to a washing treatment by flowing water washing, and then the entire surface is irradiated (post-exposure) with radiation caused by a high-pressure mercury lamp or the like to perform Decomposition treatment of the [G] acid generator remaining in the coating film. The exposure amount in this post exposure is preferably 2,000 J / m ² to 5,000 J / m ² .

[Step (C4)]

In this step, the developed coating film is heated. Specifically, the coating film is heated and fired (post-baking) by using a heating device such as a hot plate, an oven, and the like, which fires the coating film developed in step (C3). Hardening of the coating film. The firing temperature in this step is preferably 200 ° C or lower. Since a fine pattern can be formed by using radiation sensitivity and firing can be performed at such a low temperature, the forming method (3) can be applied to forming a hardened film such as an interlayer insulating film on a plastic substrate of a flexible display. The firing temperature is more preferably 120 ° C to 180 ° C, and still more preferably 120 ° C to 150 ° C. As the firing time, It depends on the type of heating equipment. For example, it can be set to 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes to 80 minutes when heat treatment is performed in an oven. In the case of heat treatment on a hot plate, it is within 30 minutes, and in the case of heat treatment in an oven, it is within 60 minutes. By doing so, a patterned coating film corresponding to a hardened film such as an interlayer insulating film can be formed on the substrate.

<Hardened film (3)>

The cured film (3) of the present invention is formed by using the aforementioned positive-type radiation-sensitive resin composition, for example, by the aforementioned method (3) for forming the cured film. The hardened film (3) is formed by using the positive-type radiation-sensitive resin composition, and therefore has good surface hardness, and can also sufficiently satisfy development adhesion, heat resistance, chemical resistance, transmittance, and relative dielectric constant. General characteristics.

<Semiconductor element>

The semiconductor element of the present invention includes the cured film (3). The semiconductor element is provided with a cured film (3) made of the positive radiation-sensitive resin composition, so that the integration degree and recording density of the circuit can be improved, and the semiconductor element can be applied to electronic devices such as display elements, LEDs, and solar cells.

<Display element>

The display element of the present invention includes the semiconductor element. The semiconductor element has a cured film (3) formed of the positive-type radiation-sensitive resin composition. This satisfies the general characteristics required for display elements in practical terms. Examples of the display element include a liquid crystal display element and the like. In the above-mentioned liquid crystal display element, for example, two sheets are formed with a liquid on the surface. The TFT array substrate of the crystal alignment film is disposed opposite to the liquid crystal alignment film side via a sealant provided on the peripheral portion of the TFT array substrate, and liquid crystal is filled between the two TFT array substrates. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the cured film as an interlayer insulating film.

[Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measurement method of each physical property value is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]

Mw and Mn were measured by gel permeation chromatography (GPC) based on the following conditions. The molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.

Device: GPC-101 (manufactured by Showa Denko)

GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (made by Shimadzu Glc)

Mobile phase: tetrahydrofuran

Column temperature: 40 ℃

Flow rate: 1.0mL / min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Detector: Differential refractometer

Standard substance: monodisperse polystyrene

<Synthesis of [A1] polymer and [A2] polymer>

The monomer compounds used in the synthesis of the polymers of the examples and comparative examples are shown below.

[Monomer compound capable of producing structural unit (I)]

Monomer compounds (1-1) to (1-10) represented by the following formulae (1-1) to (1-10)

[Monomer compound capable of producing structural unit (II-1), structural unit (II-2)]

Monomer compounds (2-1) to (2-7) represented by the following formulae (2-1) to (2-7)

[Monomer compound capable of producing structural unit (III)]

(3-1): p-hydroxyphenol methacrylate (4-hydroxyphenyl methacrylate)

(3-2): hydroxyethyl methacrylate (-2-hydroxyethyl methacrylate)

(3-3): α-methyl-p-hydroxystyrene

[Monomer compound capable of producing structural unit (IV)]

(4-1): methacrylic acid

(4-2): styrene

(4-3): methyl methacrylate

(4-4): N-cyclohexylmaleimide

(4-5): tetrahydrofurfuryl methacrylate

(4-6): Tricyclic [5.2.1.0 ^2,6 ] decane-8-yl methacrylate

[Synthesis Example 1] (Synthesis of Polymer (A-1))

In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Next, 60 parts by mass of the monomer compound (1-1) capable of generating the structural unit (I), 18 parts by mass of the monomer compound (2-1) capable of generating the structural unit (II-1), and a structural unit ( IV) 22 parts by mass of the monomer compound (4-2) was substituted with nitrogen, and the temperature of the solution was raised to 70 ° C. while gently stirring, and the temperature was maintained for 4 hours to polymerize to obtain a polymer containing (A-1) A polymer solution. The solid content concentration of this polymer solution was 30.4%, the Mw of the polymer (A-1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Synthesis Examples 2 to 46] (Synthesis of Polymers (A-2) to (A-42) and (a-1) to (a-4))

The polymers (A-2) to (A-42) and (a-1) to (a) were synthesized in the same manner as in Synthesis Example 1 except that the monomer compounds of the types and blending amounts shown in Table 1 below were used. a-4). The solid content concentration of each of the obtained polymer solutions and the Mw and Mw / Mn of each polymer were the same as those of the polymer (A-1). In addition, a blank column in Table 1 indicates that the monomer compound is not blended.

<Preparation of the resin composition (1) for hardened film formation>

[Example 1]

Diethylene glycol methyl ethyl ether as a solvent was added to a polymer solution containing (A-1) 100 parts by mass (solid content) of the [A1] polymer so that the solid content concentration became 30% by mass. The resin composition (1) for forming a cured film was prepared by filtering through a membrane filter having a pore size of 0.2 μm.

[Example 2 and Comparative Example 1]

A resin composition (1) for each cured film was prepared in the same manner as in Example 1 except that the component [A] was the type and blending amount shown in Table 2. In addition, "-" in Table 2 shows that the component was not blended or the evaluation described later was not performed.

<Preparation of negative radiation-sensitive resin composition (2)>

[B] polymerizable compound, [C] radiation sensitive polymerization initiator, and [D] antioxidant used in the preparation of each negative radiation sensitive resin composition (2) are shown below.

[[B] Polymerizable compound]

B-1: Dinepentaerythritol hexaacrylate

B-2: Mixture of polyfunctional acrylate compounds (KAYARAD DPHA-40H, manufactured by Nippon Kayaku)

B-3: 1,9-nonanediol diacrylate

B-4: ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300, manufactured by Toa Synthetic)

B-5: Succinic acid modified neopentaerythritol triacrylate

[[C] Radiation sensitive polymerization initiator]

C-1: Ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamoxime) (IRGACURE OXE02 (Made by Ciba Specialty Chemicals)

C-2: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzidine oxime)] (IRGACURE OXE01, manufactured by Ciba Specialty Chemicals)

C-3: 2-methyl-1- (4-methylphenylthio) -2- Porphyrin-1-one (IRGACURE 907, manufactured by Ciba Specialty Chemicals)

C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Porphyrin-4-yl-phenyl) -butan-1-one (IRGACURE 379, manufactured by Ciba Specialty Chemicals)

[[D] Antioxidant]

D-1: neopentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60, manufactured by ADEKA)

D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (Adekastab AO-20, manufactured by ADEKA)

[Example 3]

A polymer solution containing 100 parts by mass (solid content) of (A-1) as a [A2] polymer, 50 parts by mass of (B-1) as a [B] polymerizable compound, and radiation sensitive as [C] (C-1) 5 parts by mass of the polymerizable polymerization initiator was mixed, and diethylene glycol methyl ethyl ether was added as a solvent so that the solid content concentration became 30% by mass, and a membrane filter having a pore size of 0.2 μm was added. Filter to prepare a negative radiation-sensitive resin composition (2).

[Examples 4 to 50 and Comparative Examples 2 to 5]

In addition to the components [A], [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, and [D] antioxidant, the types shown in Table 2 and Except for the blending amount, the same procedure as in Example 3 was performed to prepare each negative-type radiation-sensitive resin composition (2). In addition, "-" in Table 2 shows that the component was not blended.

<Evaluation>

The prepared resin compositions (1) and (2) for each cured film were evaluated by the following evaluation methods. The evaluation results are shown in Table 2 together.

[Storage stability]

Each resin composition for forming a cured film was left in an oven at 40 ° C. for one week, and the viscosity before and after heating was measured to determine the viscosity change rate (%) as an index of storage stability. Set the viscosity change rate as follows: A: viscosity change rate is less than 5%, B: viscosity change rate is more than 5% and less than 10%, C: viscosity change rate is more than 10% and less than 15%, and D: viscosity change rate is more than 15%. In the case of A or B, the storage stability was evaluated as good, and in the case of C or D, it was evaluated as poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R, manufactured by Toki Sangyo).

[Sensitivity]

Using a spinner, each resin composition for curing film formation was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a pattern of lines and spaces with a width of 10 μm. Next, a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform a development treatment at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum amount of ultraviolet irradiation that can form a pattern of lines and spaces with a width of 10 μm was measured. When the measured value is less than 700 J / m ² , the sensitivity can be evaluated as good, and when the measured value is 700 J / m ² or more, it can be evaluated as poor.

[Development Adhesiveness]

Using a spinner, each resin composition for curing film formation was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays of 1,000 J / m ² by a mercury lamp through a pattern mask having a pattern of lines and spaces having a width of 10 μm. Next, a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform a development treatment at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line and space pattern with a width of 10 μm was observed with a microscope as an index of development adhesion. At this time, the following settings were made according to the degree of peeling: A: No peeling, B: Slight peeling, C: Partial peeling, D: Peeling on the entire surface. In the case of A or B, the development adhesion was evaluated as good In the case of C or D, the evaluation was bad.

[Chemical resistance]

Using a spinner, each resin composition for curing film formation was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 1,000 J / m ² . Next, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes, and the film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfine controlled at a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film after the dipping was measured, and the film thickness was calculated by the following formula The rate of change is an index of chemical resistance.

Change rate of film thickness = ((t1-T1) / T1) × 100 (%)

When the absolute value of the value is less than 5%, the chemical resistance can be evaluated as good, and when the absolute value is 5% or more, it can be evaluated as poor.

[Heat resistance]

Using a spinner, each resin composition for curing film formation was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 1,000 J / m ² . Then, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. Using a measuring device (TG / DTA220U, manufactured by SII Nano Technology), the 5% thermal weight loss temperature of the obtained cured film was measured in air, which became an index of heat resistance. At this time, when the 5% weight reduction temperature is 300 ° C or higher, heat resistance can be evaluated as good, and when less than 300 ° C, heat resistance can be evaluated as poor.

[Transmittance]

Using a spinner, each resin composition for forming a cured film was coated on a glass substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 1,000 J / m ² . Next, the glass substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet-visible spectrophotometer (V-630, manufactured by Japan Spectroscopy). At this time, the case where the transmittance of light having a wavelength of 400 nm is 95% or more can be evaluated as good (good transparency), and the case where less than 95% can be evaluated as poor (poor transparency).

[Surface hardness]

Using a spinner, each resin composition for curing film formation was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 1,000 J / m ² . Then, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. Then, regarding the substrate on which the cured film was formed, the pencil hardness of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, the surface hardness of the cured film can be evaluated as good (the resin composition for forming a cured film has sufficient curability), and when it is 2H or less, it can be evaluated as defective.

[Relative permittivity]

Using a spinner, each resin composition for hardened film formation was coated on a SUS substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Using an exposure machine (MPA-600FA, manufactured by Canon), the above coating film is exposed so that the cumulative irradiation amount becomes 1,000 J / m ² , and the exposed substrate is heated at 200 ° C. for 30 minutes in a clean oven. As a result, a cured film was formed on the SUS substrate. Next, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. About the board | substrate which has this electrode pattern, the electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and Precision LCR Meter (HP4284A, manufactured by Yokogawa Hewlett-Packard) were used, and the relative dielectric constant was measured by the CV method at a frequency of 10 kHz. In this case, a case where the relative dielectric constant is 3.9 or less can be evaluated as good, and a case where it is more than 3.9 can be evaluated as bad.

As can be seen from the evaluation results in Table 2, the characteristics of any of the examples were good, while the characteristics of any of the comparative examples were poor.

<[A3] Synthesis of Polymer>

The monomer compounds used in the synthesis of the polymers of the examples and comparative examples are shown below.

[Monomer compound capable of producing structural unit (I)]

Monomer compounds (1-1) to (1-10) represented by the following formulae (1-1) to (1-10)

[Monomer compound capable of producing structural unit (II-3)]

Monomer compounds (2-1) to (2-7) represented by the following formulae (2-1) to (2-7)

[Monomer compound capable of producing structural unit (III)]

(3-1): p-hydroxyphenyl methacrylate (4-hydroxyphenyl methacrylate)

(3-2): hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

(3-3): α-methyl-p-hydroxystyrene

[Monomer compound capable of producing structural unit (IV)]

(4-1): methacrylic acid

(4-2): styrene

(4-3): methyl methacrylate

(4-4): N-cyclohexylmaleimide

(4-5): tetrahydrofurfuryl methacrylate

(4-6): Tricyclic [5.2.1.0 ^2,6 ] decane-8-yl methacrylate

[Synthesis Example a1] (Synthesis of Polymer (A-a1))

To a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Next, 60 parts by mass of the compound (1-1) capable of generating the structural unit (I), 18 parts by mass of the compound (2-1) capable of generating the structural unit (II-3), and a compound capable of generating the structural unit (IV) were added. (4-2) 22 parts by mass was substituted with nitrogen, and the temperature of the solution was raised to 70 ° C while gently stirring, and the temperature was maintained for 4 hours to perform polymerization, thereby obtaining polymerization containing a copolymer (A-a1)物 溶液。 The solution. The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the copolymer (A-a1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Synthesis examples a2 to a45] (Synthesis of polymers (A-a2) to (A-a42) and (a-a1) to (a-a3))

A polymer (A-a2) to (A-a42) and (a-a1) to (a -a3). The solid content concentration of each of the obtained polymer solutions and the Mw and Mw / Mn of each polymer were the same as those of the polymer (A-a1). In addition, a blank column in Table 3 indicates that the monomer compound is not blended.

<Preparation of positive radiation-sensitive resin composition>

[G] acid generators used in the preparation of each positive radiation-sensitive resin composition are shown below.

[G] acid generator

G-1: Trifluoromethanesulfonic acid-1,8-naphthalenedimethylimide

G-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol (1.0 mole) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

G-3: Condensate of 1,1,1-tris (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

G-4: Compound represented by the above formula (5-1-i)

[Example a1]

A polymer solution containing 100 parts by mass (solid content) of (A-a1) as the [A3] polymer, 30 parts by mass of (G-2) as the [G] acid generator, and an adhesion aid (γ- 5 parts by mass of glycidoxypropyltrimethoxysilane, 0.5 parts by mass of a surfactant (FTX-218, manufactured by NEOS), and 0.1 parts by mass of an antioxidant (IRGANOX 1010, manufactured by BASF) were mixed, and the concentration of Diethylene glycol methyl ethyl ether was added as a [H] solvent in an amount of 30% by mass, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a positive radiation-sensitive resin composition.

[Examples a2 to a58 and Comparative examples a1 to a6]

A positive radiation-sensitive resin composition was prepared in the same manner as in Example a1, except that the [A3] polymer and the [G] acid generator were the types shown in Table 4.

<Evaluation>

Using each of the prepared positive-type radiation-sensitive resin compositions, evaluation was performed according to the following evaluation method. The evaluation results are shown in Table 4 together.

[Storage stability]

Each positive radiation-sensitive resin composition was left in an oven at 40 ° C. for one week, the viscosity before and after heating was measured, and the viscosity change rate (%) was determined as an index of storage stability. Set the viscosity change rate as follows: A: viscosity change rate is less than 5%, B: viscosity change rate is more than 5% and less than 10%, C: viscosity change rate is more than 10% and less than 15%, and D: viscosity change rate is more than 15%. In the case of A or B, the storage stability was evaluated as good, and in the case of C or D, it was evaluated as poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R, manufactured by Toki Sangyo).

[Sensitivity]

Using a spinner, each positive radiation-sensitive resin composition was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a pattern of lines and spaces with a width of 10 μm. Next, a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform a development treatment at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum amount of ultraviolet irradiation that can form a pattern of lines and spaces with a width of 10 μm was measured. When the measured value is less than 500 J / m ² , the sensitivity can be evaluated as good, and when 500 J / m ² or more, the sensitivity can be evaluated as poor.

[Development Adhesiveness]

Using a spinner, each positive radiation-sensitive resin composition was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with 500 J / m ² of ultraviolet rays by a mercury lamp through a pattern mask having a pattern of lines and spaces having a width of 10 μm. Next, a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform a development treatment at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line and space pattern with a width of 10 μm was observed with a microscope as an index of development adhesion. At this time, the following settings were made depending on the presence or absence of peeling: A: No peeling, B: Slight peeling, C: Partial peeling, D: Peeling on the entire surface, and in case of A or B, the development adhesiveness was evaluated as good In the case of C or D, the evaluation was bad.

[Chemical resistance]

Using a spinner, each positive radiation-sensitive resin composition was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 3,000 J / m ² . Next, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes, and the film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfine controlled at a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film after the dipping was measured, and the film thickness was calculated by the following formula. The rate of change is an index of chemical resistance.

Change rate of film thickness = ((t1-T1) / T1) × 100 (%)

When the absolute value of the value is less than 5%, the chemical resistance can be evaluated as good, and when the absolute value is 5% or more, it can be evaluated as poor.

[Heat resistance]

Using a spinner, each positive radiation-sensitive resin composition was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 3,000 J / m ² . Then, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. Using a measuring device (TG / DTA220U, manufactured by SII Nano Technology), the 5% thermal weight loss temperature of the obtained cured film was measured in air as an index of heat resistance. At this time, when the 5% weight reduction temperature is 300 ° C or higher, heat resistance can be evaluated as good, and when less than 300 ° C, heat resistance can be evaluated as poor.

[Transmittance]

Using a spinner, each positive radiation-sensitive resin composition was coated on a glass substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 3,000 J / m ² . Next, the glass substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet-visible spectrophotometer (V-630, manufactured by Japan Spectroscopy). In this case, a case where the transmittance of light having a wavelength of 400 nm is 95% or more can be evaluated as good (good transparency), and a case where less than 95% can be evaluated as poor (poor transparency).

[Surface hardness]

Using a spinner, each positive radiation-sensitive resin composition was coated on a silicon substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 3,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. Then, regarding the substrate on which the cured film was formed, the pencil hardness of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, the surface hardness of the cured film can be evaluated as good (the positive radiation-sensitive resin composition has sufficient curability), and when it is 2H or less, it can be evaluated as defective.

[Relative permittivity]

Using a spinner, each positive-type radiation-sensitive resin composition was coated on a SUS substrate, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Using an exposure machine (MPA-600FA, manufactured by Canon), the above coating film was exposed so that the cumulative irradiation amount became 9,000 J / m ² , and the exposed substrate was heated at 200 ° C. for 30 minutes in a clean oven to form a SUS substrate. A hardened film is formed on it. Next, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. About the board | substrate which has this electrode pattern, the electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and Precision LCR Meter (HP4284A, manufactured by Yokogawa Hewlett-Packard) were used, and the relative dielectric constant was measured by the CV method at a frequency of 10 kHz. In this case, a case where the relative dielectric constant is 3.9 or less can be evaluated as good, and a case where it is more than 3.9 can be evaluated as bad.

[Industrial availability]

The present invention can provide a thermosetting resin composition for forming a cured film, a negative-type radiation-sensitive resin composition, and a positive-type radiation-sensitive resin composition, which can be formed to have excellent surface hardness and sufficiently satisfy sensitivity, development adhesion A hardened film with general properties such as chemical resistance, chemical resistance, heat resistance, transmittance, and relative permittivity, as well as excellent storage stability. Therefore, the thermosetting resin composition for forming a cured film, the negative radiation-sensitive resin composition, the positive radiation-sensitive resin composition, the thermosetting resin composition for forming the cured film, and the negative radiation A cured film formed of a resin composition, a positive radiation-sensitive resin composition, a semiconductor element, and a display element, and a method for forming the cured film can be applied to manufacturing processes of electronic devices such as flexible displays.

Claims (6)

A positive radiation-sensitive resin composition comprising: [A3] a polymer having a structural unit (I) and a structural unit (II-3) and a structural unit (IV), the structural unit (I) comprising a member selected from The structural unit (II-3) includes at least one of a group represented by the following formula (1) and a group represented by the following formula (2), and the cyclic ether structure includes The ether structure is at least one of an ethylene oxide structure and an oxetane structure, and the structural unit (IV) contains a member selected from the group consisting of the following formulae (IV-2) to (IV-4), (IV-6) ), At least one of the groups (IV-8) ~ (IV-10); and [G] an acid generator, In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² One is a fluoroalkyl group having 1 to 4 carbon atoms. In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluoroalkyl group having 1 to 4 carbon atoms, and the formulae (IV-2) to (IV-4), (IV-6) In (IV-8) to (IV-10), R ⁹ is a hydrogen atom, a methyl group, or a trifluoromethyl group, R ^M is a hydrogen atom or a methyl group, and s is an integer from 1 to 10. The positive-type radiation-sensitive resin composition according to claim 1, further comprising an antioxidant. A method for forming a cured film, which comprises the following steps: (1) a step of forming a coating film on a substrate using a positive-type radiation-sensitive resin composition as claimed in claim 1 or 2; (2) a part of the coating film A step of irradiating radiation; (3) a step of developing the radiation irradiated coating film; and (4) a step of heating the developed coating film. A cured film formed of a positive-type radiation-sensitive resin composition as claimed in claim 1 or 2. A semiconductor device including a cured film as claimed in claim 4. A display element including the semiconductor element according to claim 5.